Malienated derivatives

ABSTRACT

This invention relates to malienated derivatives made from maleic anhydride, functionalized monomers, and one or more additional reagents, e.g., an oxygen-containing reagent (e.g., alcohol, polyol), a nitrogen-containing reagent (e.g., amine, polyamine, aminoalcohol), a metal and/or a metal compound. The invention relates to lubricants, functional fluids, fuels, dispersants, detergents and functional compositions (e.g., cleaning solutions, food compositions, etc.)

This application is a continuation-in-part under 35 U.S.C. §120 of U.S.application Ser. No. 13/281,108, filed Oct. 25, 2011. A claim ofpriority for this application under 35 U.S.C. §119(e) is hereby made tothe following U.S. provisional patent applications: U.S. Ser. No.61/510,159 filed Jul. 21, 2011; U.S. Ser. No. 61/467,273 filed Mar. 24,2011; U.S. Ser. No. 61/467,275 filed Mar. 24, 2011; U.S. Ser. No.61/467,276 filed Mar. 24, 2011; U.S. Ser. No. 61/467,279 filed Mar. 24,2011; and U.S. Ser. No. 61/467,292 filed Mar. 24, 2011. Theseapplications are incorporated herein by reference.

TECHNICAL FIELD

This invention relates to malienated derivatives, and to lubricants,functional fluids, fuels, functional additives for such lubricants,functional fluids and fuels including dispersants, detergents, and thelike, polymeric resins or plastics, adhesives, coatings,pharmaceuticals, cosmetics, personal care products, industrial cleaners,institutional cleaners, foods, beverages, oil field chemicals,agricultural chemicals, and the like.

BACKGROUND

Monomers are often mono-functional in nature. This limits potential usesfor derivatives.

SUMMARY

The malienated derivatives of the present invention may be derived froma functionalized monomer; maleic anhydride; and a nitrogen-containingreagent, an oxygen-containing reagent, a metal, a metal compound, or amixture of two or more thereof. These derivatives offer flexibility aswell as utility in a wide breadth of applications. These derivatives mayundergo high degrees of polymerization, resulting in polymers of uniquemolecular weight distributions and structural shapes, some of which mayhave use as specialty polymers to be employed in new applications. Theterm “polymer” is used herein to refer to polymers, includinghomopolymers and copolymers, as well as oligomers and co-oligomers.

The malienated derivatives may have utility in many applications andproducts, such as lubricants, functional fluids, fuels, dispersants,detergents, molded or extruded articles, pharmaceuticals, cosmetics,personal care products, adhesives, coatings, pharmaceuticals, cosmetics,personal care products, industrial cleaners, institutional cleaners,foods, beverages, oil field chemicals, agricultural chemicals, and thelike. The malienated derivatives may be used as base oils for lubricantsand functional fluids, and for providing functional additives forlubricants, functional fluids and fuels. When used as base oils, thesemalienated derivatives may be referred to as functional base oils. Thesefunctional base oils may be used in the lubricants and functional fluidsas base oils, and may also provide additional properties to thelubricant or functional fluid, such as dispersency, and the like, thatin the past would have been provided by supplemental additives. Thepresent invention may provide for an advantageous balance betweenvarious performance characteristics while selecting suitable malienatedderivatives that are compatible with acceptable manufacturingtechniques.

The functionalized monomer used in making the malienated derivatives maybe derived from a natural product, for example, a natural oil, ametathesized natural oil, carbohydrate, and the like. The functionalizedmonomer may be derived from one or more estolides. The natural oils,metathesized natural oils, carbohydrates, and estolides employed hereinmay provide the advantage of comprising or being derived from renewablesources (e.g., vegetable oils, animal fats or oils, and the like) andmay be obtained using environmentally friendly production techniqueswith less energy than conventional processes for making lubricants,functional fluids, fuels, functional additives for such lubricants,functional fluids and fuels, including dispersants and detergents,polymeric resins, adhesives, coatings, pharmaceuticals, cosmetics,personal care products, industrial cleaners, institutional cleaners,foods, beverages, oil field chemicals, agricultural chemicals, and thelike, derived from petroleum. This technology may be referred to as“green” technology.

Synthetic lubricants are commonly used in passenger car motor oils,heavy-duty diesel engine oils, marine and railroad engine lubricants,automatic transmission fluids, hydraulic fluids, gear oils, andindustrial lubricants, such as metalworking fluids and lubricatinggreases. The purpose of these oils is to provide improved friction andwear control, rapid dissipation of heat, and the dissolution of and/orfacilitating the removal of service-related contaminants. Achieving aproper balance between various performance characteristics is animportant consideration in selecting a synthetic lubricant for aparticular application. For example, polyolefin based lubricantstypically exhibit good low-temperature properties, high viscosity index,and excellent thermal stability, but poor solvency. As a result, theselubricants tend to be inadequate without the presence of additionalpolar base stock-containing components. Conversely, polar basestock-containing lubricants, such as those based on synthetic esters andvegetable oils, typically exhibit good solvency and high surfaceaffinity. However, these lubricants tend to be inadequate with respectto resistance to wear. The problem, therefore, is to provide a syntheticlubricant that exhibits both good solvency and good resistance to wearreduction characteristics. This invention provides a solution to thisproblem.

Ashless dispersants are additives used in lubricants, functional fluidsand fuels to prevent oxidation-derived deposits from impairing function.Lubricants, functional fluids and fuels that employ these additivesinclude passenger car motor oils, heavy-duty diesel engine oils, marineand railroad engine lubricants, automatic transmission fluids, gearoils, and the like, with the largest use typically being in automotiveand industrial engine oils. The amount of dispersant used in a lubricantor functional fluid depends upon the specific application but,typically, constitutes from about 0.1 percent to about 30 percent byweight of the lubricant or functional fluid. In fuels, the amount ofdispersant is typically less than in lubricants or functional fluids.The problem is to provide a dispersant having improved tendencies forsuspending the by-products of combustion (e.g., soot) and lubricant orfunctional fluid degradation (e.g., resin, varnish, lacquer and carbondeposits) in order to keep equipment surfaces and passageways clean.This invention provides a solution to this problem.

Detergents (e.g., metal-containing detergents that form ash uponcombustion) are used as additives in lubricants and functional fluids toprevent oxidation-derived deposits from separating on surfaces andimpairing function. Lubricants and functional fluids that typicallyemploy these additives include passenger car motor oils, heavy-dutydiesel engine oils, marine and railroad engine lubricants, and to alesser degree automatic transmission fluids, gear oils, and the like,with the largest use typically being in automotive and industrial engineoils. The amount of detergent used in a lubricant or functional fluiddepends upon the specific application but, typically, constitutes fromabout 0.1 percent to about 35 percent by weight of the lubricant orfunctional fluid. The problem is to provide detergents having improvedtendencies for neutralizing acidic combustion and fuel oxidation-deriveddeposit precursors, and for suspending these by-products and theirresultant salts in oil, thereby controlling corrosion and reducing theformation of surface deposits. This invention provides a solution tothis problem.

This invention relates to a malienated derivative composition derivedfrom: (i) a functionalized monomer comprising a hydrocarbyl group withone or more carbon-carbon double bonds and one or more functional groupsattached to the hydrocarbyl group, the hydrocarbyl group containing atleast about 5 carbon atoms, or from about 5 to about 30 carbon atoms, orfrom about 6 to about 30 carbon atoms, or from about 8 to about 30carbon atoms, or from about 10 to about 30 carbon atoms, or from about12 to about 30 carbon atoms, or from about 14 to about 30 carbon atoms,or from about 16 to about 30 carbon atoms, or from about 5 to about 18carbon atoms, or from about 12 to about 18 carbon atoms, or about 18carbon atoms, or from about 8 to about 12 carbon atoms, or about 10carbon atoms, the functional group comprising a carboxylic acid group ora derivative thereof, a hydroxyl group, an amino group, a carbonylgroup, a cyano group, a salt group, an amide salt group, an ester saltgroup, or a mixture of two or more thereof; (ii) maleic anhydride; and(iii) a nitrogen-containing reagent, an oxygen-containing reagent, ametal, a metal compound, or a mixture of two or more thereof. Thefunctionalized monomer may react with the maleic anhydride to form anintermediate product, and the intermediate product may then be reactedwith the nitrogen-containing reagent, oxygen-containing reagent,oxygen-containing reagent, metal and/or metal compound to form themalienated derivative. Alternatively, the nitrogen-containing reagent,oxygen-containing reagent, metal and/or metal compound may be reactedwith the maleic anhydride to form an intermediate product, and theintermediate product may then be reacted with the functionalized monomerto form the malienated derivative. The maleic anhydride may react withone or more carbon-carbon double bonds in the hydrocarbyl group. Themaleic anhydride may react in an ene reaction with one or morecarbon-carbon double bonds in the hydrocarbyl group. The maleicanhydride may react with the carbon atoms of one or more carbon-carbondouble bonds in the hydrocarbyl group.

The functionalized monomer may comprise an unsaturated carboxylic acid,anhydride, ester, amide, imide, alcohol, amine, aldehyde, ketone,nitrile, salt, amide salt, ester salt, or a mixture of two or morethereof.

The malienated derivatize may comprise an amide, imide, diamide, ester,di-ester, salt, metal salt, amine salt, amide salt, ester salt, or amixture of two or more thereof.

The hydrocarbyl group may contain one, two, three or four carbon-carbondouble bonds. The functionalized monomer may contain a carbon-carbondouble bond in the terminal position of the hydrocarbyl group. Thefunctional group may be attached to a terminal carbon atom on thehydrocarbyl group or to an internal carbon atom in the hydrocarbylgroup. The functionalized monomer may comprise methyl 9-decenoate.

The nitrogen-containing reagent may comprise ammonia, an aminecontaining one or more primary and/or secondary amino groups, amono-substituted amine, di-substituted amine, an amino-alcohol, an amineterminated poly(oxyalkylene) or a mixture of two or more thereof. Theoxygen-containing reagent may comprise an alcohol and/or polyol.

The metal may be an alkali metal, an alkaline earth metal, Group IIIAmetal, Group IVA metal, Group VA metal, transition metal, lanthanideseries metal, actinides series metal, or a mixture of two or morethereof. The metal may be Li, Na, K, Rb, Be, Mg, Ca, Sr, Ba, B, AI, Ga,In, Sn, Pb, Sb, Bi, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo, Ru,Rh, Pd, Ag, Cd, or a mixture of two or more thereof. The metal maycomprise an alkali metal, alkaline earth metal, titanium, zirconium,molybdenum, iron, copper, aluminum, zinc, or a mixture of two or morethereof.

The functionalized monomer, maleic anhydride, and an alkenyl succinicanhydride may be reacted with the nitrogen-containing reagent and/oroxygen-containing reagent to form a dispersant. The alkenyl succinicanhydride may comprise a polyisobutenyl succinic anhydride. Themalienated derivatize may be mixed with a succinimide. The succinimidemay be a polyisobutenyl succinimide.

The invention relates to a dispersant composition comprising any of theabove-discussed compositions, wherein the functionalized monomer andmaleic anhydride are reacted with a nitrogen-containing reagent and/oran oxygen-containing reagent.

This invention relates to a detergent composition comprising a neutralor overbased detergent derived from a metal or metal compound, maleicanhydride, and any of the above-discussed functionalized monomers. Themetal may comprise an alkali metal, alkaline earth metal, titanium,zirconium, molybdenum, iron, copper, aluminum, zinc, or a mixture of twoor more thereof. In an embodiment, one or more alkarylsulfonic acids(e.g., alkylbenzenesulfonic acids) may be mixed with the functionalizedmonomer and maleic anhydride when making the malienated derivative. Thedetergent may be derived from (1) the reaction product of thefunctionalized monomer and maleic anhydride, optionally, in combinationwith an alkaryl sulfonic acid, and (2) a reaction medium, (3) astoichiometric excess of the metal or metal compound, (4) a promoter,and (5) an acidic material. The detergent may comprise aboron-containing overbased detergent composition.

This invention relates to a concentrate composition comprising fromabout 0.1% to about 99% by weight, or from about 10% to about 90% byweight, of any of the above-discussed compositions, and a normallyliquid diluent.

This invention relates to a lubricant or functional fluid compositioncomprising any of the above-discussed malienated derivatives. Thelubricant or functional fluid composition may further comprise an APIGroup I, Group II, Group III, Group IV, Group V base oil, natural oil,estolide, or a mixture of two or more thereof. The lubricant orfunctional fluid composition may further comprise a supplementaldetergent, supplemental dispersant, corrosion inhibitor, oxidationinhibitor, antiwear agent, friction modifier, pourpoint depressant,anti-foam agent, metal deactivator, viscosity modifier, extreme pressureagent, demulsifier, seal swelling agent, or a mixture of two or morethereof. The lubricant or functional fluid composition may comprise agrease composition, the grease composition comprising lithium hydroxide,lithium hydroxide monohydrate, or a mixture thereof.

This invention relates to a fuel composition comprising any of theabove-discussed malienated derivatives. The fuel composition may furthercomprise a normally liquid fuel. The normally liquid fuel may be derivedfrom petroleum, crude oil, a Fischer-Tropsch process, coal, natural gas,oil shale, biomass, or a mixture of two or more thereof. The normallyliquid fuel may comprise a synthetic fuel. The fuel composition maycomprise gasoline, a middle distillate fuel. The fuel compositioncomprises kerosene, jet fuel, diesel fuel, fuel oil, heating oil,naphtha, or a mixture of two or more thereof. The fuel composition mayfurther comprise: one or more functional additives, the one or morefunctional additives, comprising a cold flow improver additive forincreasing horsepower; additive for improving fuel economy; additive forlubricating and reducing wear of engine components; additive forcleaning and preventing deposit buildup; additive for reducing smoke andparticulate emissions; additive for removing water; additive forreducing rust and corrosion; additive for upgrading and stabilizing thefuel; additive for improving storage and combustion capabilities;antioxidant; antistatic agent; corrosion inhibitor; fuel system icinginhibitor; cold flow improver; biocide; metal deactivator; additive forreducing fuel line and filter clogging; additive for improving fuelatomization; additive for reducing deposits on burner nozzles; additivefor enhancing flame stabilization; additive for improving combustion;additive for reducing soot formation; additive for neutralizing vanadiumand sodium; additive for improving heat transfer; additive for reducingthe formation of sulfur trioxide; additive for reducing stacktemperatures; additive for reducing carbon monoxide, oxygen and/orunburnt hydrocarbon in stack gases; additive for reducing fuelconsumption; polar compound for dispersing paraffins; oil-solubleamphiphile; pour point depressant; dewaxing additive; sludge inhibitor;dehazer; additive for reducing cloud point; or a mixtures of two or morethereof.

This invention relates to a composition comprising the malienatedderivative and further comprising water, solvent, thixotropic additive,pseudoplastic additive, rheology modifier, anti-settling agent, levelingagent, defoamer, pigment, dye, plasticizer, viscosity stabilizer,biocide, viricide, fungicide, crosslinker, humectant, surfactant,detergent, soap, fragrance, sweetener, alcohol, food product, foodadditive, or a mixture of two or more thereof. This composition is inthe form of a liquid, a solid, or a mixture thereof.

The functionalized monomer may be derived from a natural product. Thenatural product may comprise a natural oil such as vegetable oil, algaeoil, fungus oil, animal oil or fat, tall oil, or a mixture of two ormore thereof. The natural product may comprise one or morecarbohydrates. The carbohydrates may comprise one or moremonosaccharides, disaccharides, oligosaccharides and/or polysaccharides,including sucrose, lactose, glucose, fructose, and the like. The naturalproduct may comprise one or more of grass, green plants, starches,crops, grains, lignocellulosic feeds, wood, forest harvesting residues,barks, sawdust, pulping liquors, fibers, agricultural wastes, cropresidues, industrial organic wastes, and the like.

The functionalized monomer may comprise a natural product or natural oilderived unsaturated fatty acid, unsaturated fatty ester, polyunsaturatedfatty acid, polyunsaturated fatty ester, or a mixture of two or morethereof. The functionalized monomer may comprise a natural product ornatural oil derived unsaturated monoglyceride, unsaturated diglyceride,unsaturated triglyceride, or a mixture of two or more thereof.

The functionalized monomer may be derived from a natural oil, thenatural oil comprising vegetable oil, algae oil, fungus oil, animal oilor fat, tall oil, sucrose, lactose, glucose, fructose, or a mixture oftwo or more thereof.

The functionalized monomer may be derived from a natural oil, thenatural oil comprising refined, bleached and/or deodorized natural oil.The refined, bleached and/or deodorized natural oil may compriserefined, bleached and/or deodorized soybean oil.

The functionalized monomer may comprise an estolide. The functionalizedmonomer may be derived from an estolide.

The functionalized monomer may be derived from a metathesized naturaloil or natural oil derived unsaturated carboxylic acid and/or ester, themetathesized natural oil or natural oil derived unsaturated carboxylicacid and/or ester comprising the product of a self-metathesis process ora cross-metathesis process. The metathesized natural oil or natural oilderived unsaturated carboxylic acid and/or ester may be made by reactingone or more natural oils and/or natural oil derived unsaturatedcarboxylic acids and/or esters in the presence of a metathesis catalystto form the metathesized natural oil or natural oil derived unsaturatedcarboxylic acid and/or ester. The metathesized natural oil may be madeby reacting (a) one or more natural oils and/or natural oil derivedunsaturated carboxylic acids and/or esters with (b) another olefiniccompound in the presence of a metathesis catalyst. The metathesizednatural oil may be made by reacting a natural oil and/or natural oilderived unsaturated carboxylic acid and/or ester in the presence of ametathesis catalyst to form a first metathesized natural oil; and thenreacting the first metathesized natural oil in a self-metathesisreaction to form another metathesized natural oil, or reacting the firstmetathesized natural oil in a cross-metathesis reaction with a naturaloil and/or natural oil derived unsaturated carboxylic acid and/or esterto form another metathesized natural oil. The metathesized natural oilmay be formed in the presence of a metathesis catalyst, the metathesiscatalyst comprising a metal carbene catalyst based upon ruthenium,molybdenum, osmium, chromium, rhenium, and/or tungsten. The natural oilor natural oil derived unsaturated carboxylic acid and/or ester may bepartially hydrogenated prior to the reaction in the presence of themetathesis catalyst. The metathesized natural oil or natural oil derivedunsaturated carboxylic acid and/or ester may comprise from 1 to about100, or from 2 to about 50, or from 2 to about 30, or from 2 to about 10metathesis repeating groups.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates an exemplary self-metathesis reaction scheme.

FIG. 2 illustrates an exemplary cross-metathesis reaction scheme.

FIG. 3 is a flow sheet showing a metathesis process for metathesizingnatural oil, and then treating the resulting metathesized natural oil.

DETAILED DESCRIPTION

All ranges and ratio limits disclosed in the specification and claimsmay be combined in any manner. It is to be understood that unlessspecifically stated otherwise, references to “a,” “an,” and/or “the” mayinclude one or more than one, and that reference to an item in thesingular may also include the item in the plural.

The term “functional group” is used herein to refer to a group of atomsin a molecule that is responsible for a characteristic chemical reactionof that molecule. The functional group may comprise a carboxylic acidgroup or derivative thereof, a hydroxyl group, an amino group, acarbonyl group, a cyano group, or a mixture of two or more thereof. Thefunctional group may also comprise a carbon-carbon double bond.

The term “functionalized monomer” refers to a monomer comprising ahydrocarbyl group and one or more functional groups attached to thehydrocarbyl group, the hydrocarbyl group containing one or more (e.g., 1to about 4, or 1 to about 3, or 1 to about 2, or 1) carbon-carbon doublebonds, at least about 5 carbon atoms, or from about 5 to about 30 carbonatoms, or from about 6 to about 30 carbon atoms, or from about 8 toabout 30 carbon atoms, or from about 10 to about 30 carbon atoms, orfrom about 12 to about 30 carbon atoms, or from about 14 to about 30carbon atoms, or from about 16 to about 30 carbon atoms, or from about 5to about 18 carbon atoms, or from about 12 to about 18 carbon atoms, orabout 18 carbon atoms, or from about 8 to about 12 carbon atoms, orabout 10 carbon atoms. The functional group may comprise a carboxylicacid group or derivative thereof, a hydroxyl group, an amino group, acarbonyl group, a cyano group, or a mixture of two or more thereof. Thefunctionalized monomer may contain from 1 to about 4 functional groups,or from 1 to about 3, or 1 to about 2, or 1 functional group. Examplesof such functionalized monomers may include alkene substitutedcarboxylic acids, alkene substituted carboxylic esters (e.g.,unsaturated fatty acids and fatty esters), alkene-substituted carboxylicacid anhydrides, alkene substituted alcohols, alkene substituted amines,alkene substituted aldehydes, alkene substituted amides, alkenesubstituted imides, mixtures of two or more thereof, and the like. Thefunctionalized monomer may comprise an ester derived from thetransesterification of an alkene substituted carboxylic ester with analcohol. The functionalized monomer may be referred to as beingdifunctional or polyfunctional since it has at least one carbon-carbondouble bond and at least one functional group.

The terms “hydrocarbyl” or “hydrocarbyl group,” when referring to groupsattached to the remainder of a molecule, refer to one or more groupshaving a purely hydrocarbon or predominantly hydrocarbon character.These groups may include: (1) purely hydrocarbon groups (i.e.,aliphatic, alicyclic, aromatic, aliphatic- and alicyclic-substitutedaromatic, aromatic-substituted aliphatic and alicyclic groups, as wellas cyclic groups wherein the ring is completed through another portionof the molecule (that is, any two indicated substituents may togetherform an alicyclic group)); (2) substituted hydrocarbon groups (i.e,groups containing non-hydrocarbon substituents such as hydroxy, amino,nitro, cyano, alkoxy, acyl, halo, etc.); and (3) hetero groups (i.e.,groups which contain atoms, such as N, O or S, in a chain or ringotherwise composed of carbon atoms). In general, no more than aboutthree substituents or hetero atoms, or no more than one, may be presentfor each 10 carbon atoms in the hydrocarbyl group. The hydrocarbyl groupmay contain one, two, three or four carbon-carbon double bonds.

The term “carboxylic acid group or derivative thereof” refers to acarboxylic acid group (e.g., —COOH), or a group that may be derived froma carboxylic acid group, including a carboxylic acid anhydride group, acarboxylic ester group (e.g., —COOR), amide group (e.g., —CONR₂), imidegroup (e.g., —CONRCO—), carbonyl or keto group (e.g., —COR), aldehyde orformyl group (e.g., —CHO), or a mixture of two or more thereof. Themethods used to form these derivatives may include one or more ofaddition, neutralization, overbasing, saponification,transesterification, esterification, amidification, hydrogenation,isomerization, oxidation, alkylation, acylation, sulfurization,sulfonation, rearrangement, reduction, fermentation, pyrolysis,hydrolysis, liquefaction, anaerobic digestion, hydrothermal processing,gasification, or a combination of two or more thereof. In the foregoingformulas, R may be hydrogen or a hydrocarbyl group. When the carboxylicacid derivative group is bivalent, such as with anhydrides or imides,two hydrocarbyl groups may be attached, at least one of hydrocarbylgroups containing from about 5 to about 30 carbon atoms, or from about 6to about 30 carbon atoms, or from about 8 to about 30 carbon atoms, orfrom about 10 to about 30 carbon atoms, or from about 12 to about 30carbon atoms, or from about 14 to about 30 carbon atoms, or from about16 to about 30 carbon atoms, or from about 5 to about 18 carbon atoms,or from about 12 to about 18 carbon atoms, or about 18 carbon atoms.

The term “unsaturated carboxylic acid or derivative thereof” refers toan unsaturated carboxylic acid, or an unsaturated carboxylic acidanhydride, ester, amide, imide, aldehyde, ketone, or a mixture of two ormore thereof, that may be derived from the unsaturated carboxylic acid.

The term “unsaturated fatty acid or derivative thereof” refers to anunsaturated fatty acid, or an unsaturated fatty anhydride, ester, amide,imide, aldehyde, ketone, or a mixture of two or more thereof, that maybe derived from the unsaturated fatty acid.

The term “olefin” is used herein to refer to a compound containing oneor more carbon-carbon double bonds. The olefin may be a monoene (e.g.,ethene), diene (e.g., butadiene), triene (e.g., octatriene), tetraene(e.g., fanesene), or a mixture of two or more thereof. The olefin may bea conjugated diene (e.g., 1,3-butadiene).

The term “olefin comonomer” refers to an olefin of from 2 to about 30carbon atoms, or from 2 to about 24 carbon atoms, or from about 4 toabout 24 carbon atoms, or from about 6 to about 24 carbon atoms. Theolefin may comprise an alpha olefin, an internal olefin, or a mixturethereof. The internal olefin may be symmetric or asymmetric. The olefinmay be linear or branched. The olefin may comprise a monoene, diene,triene, tetraene, or a mixture of two or more thereof. The monoenes maycomprise one or more of ethene, 1-propene, 1-butene, 2-butene,isobutene, 1-pentene, 2-pentene, 3-pentene, cyclopentene, 1-hexene,2-hexene, 3-hexene, cyclohexene, 1-heptene, 2-heptene, 3-heptene,1-octene, 2-octene, 3-octene, 1-nonene, 2-nonene, 3-nonene, 4-nonene,1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-octadecene, 1-eicosene,2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene,2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene,2-methyl-3-pentene, 2,2-dimethyl-3-pentene, styrene, vinyl cyclohexane,or a mixture of two or more thereof. The dienes, trienes and tetraenesmay comprise butadiene, isoprene, hexadiene, decadiene, octatriene,ocimene, farnesene, tetraeicosene, or a mixture of two or more thereof.The dienes may include conjugated dienes, examples of which may include1,3-butadiene, 1,3-pentadiene, mixtures thereof, and the like.

The term “normally liquid fuel” is used herein to refer to a fuel thatis liquid at atmospheric pressure and at the temperature at which it islikely to be stored or used. These may include gasoline and middledistillate fuels. The normally liquid fuels are distinguished from solidfuels such as coal and gaseous fuels such as natural gas.

The term “natural product” is used herein to refer to products ofnature, including natural oil, carbohydrates, and the like.

The term “natural oil” refers to oils or fats derived from plants oranimals. The term “natural oil” includes natural oil derivatives, unlessotherwise indicated, and such natural oil derivatives may include one ormore natural oil derived unsaturated carboxylic acids or derivativesthereof. The natural oils may include vegetable oils, algae oils, fungusoils, animal oils or fats, tall oils, derivatives of these oils,combinations of two or more of these oils, and the like. The naturaloils may include, for example, canola oil, rapeseed oil, coconut oil,corn oil, cottonseed oil, olive oil, palm oil, peanut oil, saffloweroil, sesame oil, soybean oil, sunflower seed oil, linseed oil, palmkernel oil, tung oil, jatropha oil, mustard oil, camellina oil,pennycress oil, castor oil, coriander oil, almond oil, wheat germ oil,bone oil, lard, tallow, poultry fat, yellow grease, fish oil, mixturesof two or more thereof, and the like. The natural oil (e.g., soybeanoil) may be refined, bleached and/or deodorized.

The terms “natural product derived unsaturated carboxylic acids and/orderivatives thereof” and “natural oil derived unsaturated carboxylicacid and/or derivatives thereof” refer to unsaturated carboxylic acid'sor derivatives thereof derived from natural products or natural oil,respectively. The methods used to form these derivatives may include oneor more of addition, neutralization, overbasing, saponification,transesterification, esterification, amidification, partialhydrogenation, isomerization, oxidation, alkylation, acylation,sulfurization, sulfonation, rearrangement, reduction, fermentation,pyrolysis, hydrolysis, liquefaction, anaerobic digestion, hydrothermalprocessing, gasification, or a combination of two or more thereof.Examples of natural oil derived unsaturated carboxylic acids orderivatives thereof may include gums, phospholipids, soapstock,acidulated soapstock, distillate or distillate sludge, unsaturated fattyacids, unsaturated fatty acid esters, as well as hydroxy substitutedvariations thereof. The unsaturated carboxylic acid or derivativethereof, may comprise an alkene chain in the carboxylic acid orderivative portion of the molecule of at least about 5 carbon atoms, orfrom about 5 to about 30 carbon atoms, or from about 6 to about 30carbons, or from about 8 to about 30 carbon atoms, or from about 10 toabout 30 carbon atoms, or from about 12 to about 30 carbon atoms, orfrom about 14 to about 30 carbons, or from about 16 to about 30 carbonatoms, or from about 0.5 to about 18 carbon atoms, or from about 6 toabout 24 carbon atoms, or from about 6 to about 18 carbon atoms, or fromabout 8 to about 24 carbon atoms, or from about 8 to about 18 carbonatoms, or from about 10 to about 24 carbon atoms, or from about 10 toabout 18 carbon atoms, or from about 12 to about 24 carbon atoms, orfrom about 12 to about 18 carbon atoms, or from about 16 to about 20carbon atoms, or from about 12 to about 18 carbon atoms, or from about15 to about 18 carbon atoms, or about 18 carbon atoms, or from about 8to about 12 carbon atoms, or about 10 carbon atoms, with one or morecarboxylic acid and/or ester groups, and at least one carbon-carbondouble bond in the alkene chain. The unsaturated carboxylic acid orderivative thereof may contain an alkene chain with 1 to about 4, or 1to about 3, or 1 or 2, or 1 carbon-carbon double bond in the alkenechain. The natural product derived or natural oil derived unsaturatedcarboxylic acid or derivative thereof may comprise an unsaturated fattyacid alkyl (e.g., methyl) ester derived from a glyceride (e.g., atriglyceride) of the natural product or natural oil.

The natural oil may comprise a refined, bleached and/or deodorizednatural oil, for example, a refined, bleached, and/or deodorized soybeanoil (i.e., RBD soybean oil). Soybean oil may comprises about 95% byweight or greater (e.g., 99% weight or greater) triglycerides of fattyacids. The fatty acids in the soybean oil may include saturated fattyacids, including palmitic acid (hexadecanoic acid) and stearic acid(octadecanoic acid), and unsaturated fatty acids, including oleic acid(9-octadecenoic acid), linoleic acid (9,12-octadecadienoic acid), andlinolenic acid (9,12,15-octadecatrienoic acid).

The term “carbohydrate” is used herein to refer to a class of compoundswith the empirical formula C_(m)(H₂O)_(n) that comprise carbon, hydrogenand oxygen atoms, with a hydrogen:oxygen ratio of 2:1. An example isdeoxyribose which has the empirical formula C₅H₁₀O₄. The carbohydratesinclude the saccharides. The saccharides may include: monosaccharides,disaccharides, oligosaccharides, and polysaccharides. Themonosaccharides and disaccharides may be referred to as sugars. Thesugars, which may be in the form of crystalline carbohydrates, mayinclude sucrose, lactose, glucose, fructose, fruit sugar, and the like.These may be obtained from sugar cane, sugar beet, corn syrup, and thelike.

The term “estolide” refers to natural and synthetic compounds derivedfrom fats and oils, e.g., renewable vegetable and animal based oils. Theestolide structure may be identified by a secondary ester linkage of onefatty acyl molecule to the alkyl backbone of another fatty acidfragment. Estolides may be free acids or esters, or they may be foundwithin a triglyceride structure. The later form of estolide may occurnaturally in the genus lesquerella where the species lesquerellaauriculata may produce up to about 96% of its seed oil as estolides.Triglyceride estolides may be synthesized from castor and lesquerellaoils. Estolides may be synthesized from unsaturated fatty acids. Theestolides may include natural and synthetic glyceride estolides, andestolides derived from fatty acids, including hydroxy fatty acids,unsaturated fatty acids and epoxy fatty acids. These are discussed inIsabell, “Chemistry and Physical Properties of Estolides,” Grasas YAcertes, 62 (1), Enero-Marzo, 8-20, 2011, ISSN: 0017-3495, DOI:10.3989/gya 010810, which is incorporated herein by reference.

The unsaturated carboxylic (e.g., fatty) acid or derivative thereof maybe functionalized at one or more double bonds in the alkene chain byreacting it with an enophilic reagent. The enophilic reagent maycomprise an enophilic acid reagent, an oxidizing agent, an aromaticcompound, a sulfurizing agent, a hydroxylating agent, a halogenatingagent, or a mixture of two or more thereof.

The term “another olefinic compound” is used herein to refer to anatural oil, a natural oil derived unsaturated carboxylic acid orderivative thereof, or one of the above-described olefin comonomers.

The term “metathesis reaction” refers to a catalytic reaction whichinvolves the interchange of alkylidene units among compounds containingone or more carbon-carbon double bonds (e.g., olefinic compounds) viathe formation and cleavage of the carbon-carbon double bonds. Metathesismay occur between two like molecules (often referred to asself-metathesis) and/or between two different molecules (often referredto as cross-metathesis).

The term “metathesis catalyst” refers to any catalyst or catalyst systemthat catalyzes a metathesis reaction.

The terms “metathesize” and “metathesizing” refer to the reacting of oneor more reactant compounds (e.g., a natural oil or natural oil derivedunsaturated carboxylic acid or derivative thereof) in the presence of ametathesis catalyst to form a metathesized product (e.g., metathesizednatural oil) comprising one or more metathesis monomers, oligomersand/or polymers. Metathesizing may refer to self-metathesis orcross-metathesis. For example, metathesizing may refer to reacting twotriglycerides present in a natural oil (self-metathesis) in the presenceof a metathesis-catalyst, wherein each triglyceride has an unsaturatedcarbon-carbon double bond, thereby forming a monomer, oligomer and/orpolymer containing bonded groups derived from the triglycerides. Thenumber of metathesis bonded groups in the metathesized monomers,oligomers and/or polymers may range from 1 to about 100, or from 2 toabout 50, or from 2 to about 30, or from 2 to about 10. These mayinclude metathesis monomers, metathesis dimers, metathesis trimers,metathesis tetramers, metathesis pentamers, as well as high ordermetathesis oligomers (e.g., metathesis hexamers, heptamers, octamers,nonamers, decamers, and the like).

The term “metathesized natural oil” refers to the product formed fromthe metathesis reaction of a natural oil (or a natural oil derivedunsaturated carboxylic acid or derivative thereof) in the presence of ametathesis catalyst to form one or more functionalized olefins and/orolefins comprising one or more metathesis monomers, oligomers and/orpolymers derived from the natural oil. The number of metathesis bondedgroups in the metathesized natural oil monomers, oligomers and/orpolymers may range from 1 to about 100, or from 2 to about 50, or from 2to about 30, or from 2 to about 10. These may include one or moremetathesis monomers, metathesis dimers, metathesis trimers, metathesistetramers, metathesis pentamers, and higher order metathesis oligomersor polymers (e.g., metathesis hexamers, heptamers, octamers, nonamers,decamers, and the like). The metathesized natural oil may be partiallyhydrogenated, forming a “partially hydrogenated metathesized naturaloil.” The partial hydrogenation step may be conducted prior to orsubsequent to the metathesis reaction. The metathesized natural oil maybe epoxidized. The metathesized natural oil may be formed from themetathesis reaction of a natural oil comprising more than one naturaloil (e.g., a mixture of soybean oil and palm oil). The metathesizednatural oil may be formed from the metathesis reaction of a natural oilcomprising a mixture of one or more natural oils and one or more naturaloil derivatives. The metathesized natural oil may be in the form of aliquid or a solid. The solid may comprise a wax.

The term “metathesized natural oil derived unsaturated carboxylic acid”refers to an unsaturated carboxylic acid or a derivative thereof derivedfrom a metathesized natural oil.

The term “metathesized natural oil derivative” refers to the productmade by the reaction of a metathesized natural oil with anitrogen-containing reagent, an oxygen-containing reagent, and/or anenophilic reagent. The enophilic reagent may comprise an enophilic acidreagent, oxidizing agent, sulfurizing agent, aromatic compound,hydroxylating agent, halogenating agent, or a mixture of two or morethereof. The metathesized natural oil derivative may be in the form of aliquid or a solid, and may be oil soluble and/or fuel soluble. The solidmay comprise a wax.

The term “metathesis monomer” refers to a single entity that is theproduct of a metathesis reaction which comprises a molecule of acompound with one or more carbon-carbon double bonds which has undergonean alkylidene unit interchange via one or more of the carbon-carbondouble bonds either within the same molecule (intramolecular metathesis)and/or with a molecule of another compound containing one or morecarbon-carbon double bonds such as an olefin (intermolecularmetathesis).

The term “metathesis dimer” refers to the product of a metathesisreaction wherein two reactant compounds, which can be the same ordifferent and each with one or more carbon-carbon double bonds, arebonded together via one or more of the carbon-carbon double bonds ineach of the reactant compounds as a result of the metathesis reaction.

The term “metathesis trimer” refers to the product of one or moremetathesis reactions wherein three molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the trimer containing threebonded groups derived from the reactant compounds.

The term “metathesis tetramer” refers to the product of one or moremetathesis reactions wherein four molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the tetramer containing fourbonded groups derived from the reactant compounds.

The term “metathesis pentamer” refers to the product of one or moremetathesis reactions wherein five molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the pentamer containing fivebonded groups derived from the reactant compounds.

The term “metathesis hexamer” refers to the product of one or moremetathesis reactions wherein six molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the hexamer containing sixbonded groups derived from the reactant compounds.

The term “metathesis heptamer” refers to the product of one or moremetathesis reactions wherein seven molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the heptamer containing sevenbonded groups derived from the reactant compounds.

The term “metathesis octamer” refers to the product of one or moremetathesis reactions wherein eight molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the octamer containing eightbonded groups derived from the reactant compounds.

The term “metathesis nonamer” refers to the product of one or moremetathesis reactions wherein nine molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the nonamer containing ninebonded groups derived from the reactant compounds.

The term “metathesis decamer” refers to the product of one or moremetathesis reactions wherein ten molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the decamer containing tenbonded groups derived from the reactant compounds.

The term “metathesis oligomer” refers to the product of one or moremetathesis reactions wherein two or more molecules (e.g., 2 to about 10,or 2 to about 4) of two or more reactant compounds, which can be thesame or different and each with one or more carbon-carbon double bonds,are bonded together via one or more of the carbon-carbon double bonds ineach of the reactant compounds as a result of the one or more metathesisreactions, the oligomer containing a few (e.g., 2 to about 10, or 2 toabout 4) bonded groups derived from the reactant compounds.

The term “metathesis polymer” refers to the product of one or moremetathesis reactions wherein many molecules of two or more reactantcompounds, which can be the same or different and each with one or morecarbon-carbon double bonds, are bonded together via one or more of thecarbon-carbon double bonds in each of the reactant compounds as a resultof the one or more metathesis reactions, the polymer containing morethan one (e.g., 2 to about 100, or 2 to about 50, or 2 to about 10, or 2to about 4) bonded groups derived from the reactant compounds.

The term “oil soluble” is used herein to refer to a material which issoluble in mineral oil to the extent of at least about 10 grams of thematerial per liter of mineral oil at a temperature of 20° C., or atleast about 1% by weight.

The term “fuel soluble” is used herein to refer to a material which issoluble in a normally liquid fuel (e.g., gasoline and/or middledistillate) to the extent of at least about 100 mg of the material perliter of the normally liquid fuel at a temperature of 20° C.

The Functionalized Monomer

The functionalized monomer may comprise an unsaturated hydrocarbyl groupwith one or more attached functional groups. The hydrocarbyl group maybe an alkene group. The hydrocarbyl group may contain at least about 5carbon atoms, or from about 5 to about 30 carbon atoms, or from about 5to about 18 carbon atoms, or from about 6 to about 30 carbons, or fromabout 8 to about 30 carbon atoms, or from about 10 to about 30 carbonatoms, or from about 12 to about 30 carbon atoms, or from about 14 toabout 30 carbons, or from about 16 to about 30 carbon atoms, or fromabout 8 to about 24 carbon atoms, or from about 10 to about 24 carbonatoms, or from about 12 to about 24 carbon atoms, or from about 8 toabout 20 carbon atoms, or from about 10 to about 20 carbon atoms, orfrom about 12 to about 20 carbon atoms, or from about 12 to about 18carbon atoms, or from about 14 to about 18 carbon atoms, or from about15 to about 18 carbon atoms, or from about 16 to about 18 carbon atoms,or about 18 carbon atoms, or from about 8 to about 12 carbon atoms, orabout 10 carbon atoms. The hydrocarbyl group may be monounsaturated orpolyunsaturated with from 1 to about 4 carbon-carbon double bonds, orfrom 1 to about 3 carbon-carbon double bonds, or from 1 to about 2carbon-carbon double bonds, or 1 carbon-carbon double bond. Thehydrocarbyl group may contain a carbon-carbon double bond in theterminal position of the hydrocarbyl group (e.g., 1-pentenyl,1-heptenyl, 1-decenyl, 1-dodecnyl, 1-octadecenyl, and the like), and/orone or more internal carbon-carbon double bonds. The hydrocarbyl groupmay be linear or branched and may optionally include one or morefunctional groups in addition to the carboxylic acid group or derivativethereof. For example, the hydrocarbyl group may include one or morehydroxyl groups.

The functional group may comprise a carboxylic acid group or derivativethereof, a hydroxyl group, an amino group, a carbonyl group, a cyanogroup, or a mixture of two or more thereof. The functional group may beattached to a terminal carbon atom on the hydrocarbyl group and/or on aninternal carbon atom. The functionalized monomer may contain from 1 toabout 4 functional groups, or from 1 to about 3 functional groups, or 1to about 2 functional groups, or 1 functional group.

The functionalized monomer may have one or more additional functionalgroups attached to the hydrocarbyl group. These may be provided byreacting the functionalized monomer with an enophilic reagent which mayreact on the hydrocarbyl group, or may be reactive towards one or moreof the carbon-carbon double bonds in the hydrocarbyl group, and/or thefunctional group. The enophilic reagent may be an enophilic acid,anhydride and/or ester reagent, an oxidizing agent, an aromaticcompound, a sulfurizing agent, a hydroxylating agent, a halogenatingagent, or a mixture of two or more thereof. These functionalizedmonomers may be referred to as enophilic reagent modified functionalizedmonomers or polyfunctionalized monomers.

The functionalized monomer, or polymer derived from the functionalizedmonomer, may comprise an ester salt and/or a carboxylic salt. The saltportion of the compound may be derived from ammonia, an amine, apolyamine, an aminoalcohol, amine terminated poly(oxyalkylene), and/or ametal. Any of ammonia, or the amines, polyamines, aminoalcohols and/oramine terminated poly(oxyalkylenes) discussed below may be used. Themetal may be an alkali metal (e.g., a Group IA metal such as Li, Na, K,Rb, and Cs); alkaline earth metal (e.g., Group IIA metals such as Be,Mg, Ca, Sr, and Ba); Group IIIA metal (e.g., B, Al, Ga, In, and Tl);Group IVA metal (e.g., Sn and Pb), Group VA metal (e.g., Sb and Bi),transition metal (e.g., Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo,Ru, Rh, Pd, Ag and Cd), lanthanide or actinides, or a mixture of two ormore thereof. The metal may comprise an alkali metal, alkaline earthmetal, titanium, zirconium, molybdenum, iron, copper, aluminum, zinc, ora mixture of two or more thereof.

The functionalized monomer may be derived from one or more naturalproducts, including natural oil, metathesized natural oil,carbohydrates, and the like. The functional monomer may be derived fromor comprise an estolide. The functionalized monomer may be derived fromor comprise a metathesized polyol ester, for example, a metathesizedmonoglyceride, metathesized diglyceride, metathesized triglyceride, amixture of two or more thereof, and the like. An advantage of employinga metathesized natural oil is that the structure of the functionalizedmonomer may be tailored as a result of the metathesis process. Forexample, it may be advantageous to employ a functionalized monomer witha carbon-carbon double bond in the terminal position of the structuralbackbone of the compound. This may be possible to achieve with themetathesis process. Also, with metathesis, olefins may be separated fromthe carboxylic acids or derivatives thereof.

The natural oil may comprise one or more oils or fats derived fromplants and/or animals. The natural oils may include vegetable oils,algae oils, fungus oils, animal oils or fats, tall oils, derivatives ofthese oils, combinations of two or more of these oils, and the like. Thenatural oils may include canola oil, rapeseed oil, coconut oil, cornoil, cottonseed oil, olive oil, palm oil, peanut oil, safflower oil,sesame oil, soybean oil, sunflower seed oil, linseed oil, palm kerneloil, tung oil, jatropha oil, mustard oil, camellina oil, pennycress oil,castor oil, tall oil, coriander oil, almond oil, wheat germ oil, boneoil, lard, tallow, poultry fat, yellow grease, fish oil, bone oil,mixtures of two or more thereof, and the like. The natural oil may berefined, bleached and/or deodorized.

The natural oil may comprise soybean oil. Soybean oil may compriseunsaturated glycerides, for example, in many embodiments about 95%weight or greater (e.g., 99% weight or greater) triglycerides. Majorfatty acids making up soybean oil may include saturated fatty acids,palmitic acid (hexadecanoic acid) and stearic acid (octadecanoic acid),and unsaturated fatty acids, oleic acid (9-octadecenoic acid), linoleicacid (9,12-octadecadienoic acid), and linolenic acid(9,12,15-octadecatrienoic acid). Soybean oil may be a highly unsaturatedvegetable oil with many of the triglyceride molecules having at leasttwo unsaturated fatty acids.

The functionalized monomer may comprise an unsaturated carboxylic acidor derivative thereof (e.g., anhydride, ester, aminde or imide), or anunsaturated alcohol, amine, aldehyde, ketone, nitrile, or a mixture oftwo or more thereof. The unsaturated monomer may comprise a hydrocarbylgroup (e.g., an alkene chain) of at least about 5 carbon atoms, or fromabout 5 to about 30 carbon atoms, or from about 5 to about 18 carbonatoms, or from about 6 to about 30 carbons, or from about 8 to about 30carbon atoms, or from about 10 to about 30 carbon atoms, or from about12 to about 30 carbon atoms, or from about 14 to about 30 carbons, orfrom about 16 to about 30 carbon atoms, or from about 8 to about 24carbon atoms, or from about 10 to about 24 carbon atoms, or from about12 to about 24 carbon atoms, or from about 8 to about 20 carbon atoms,or from about 10 to about 20 carbon atoms, or from about 12 to about 20carbon atoms, or from about 12 to about 18 carbon atoms, or from about14 to about 18 carbon atoms, or from about 15 to about 18 carbon atoms,or from about 16 to about 18 carbon atoms, or about 18 carbon atoms, orfrom about 8 to about 12 carbon atoms, or about 10 carbon atoms, withone or more functional groups, and at least one carbon-carbon doublebond in the hydrocarbyl group or alkene chain. The unsaturatedcarboxylic acid or derivative thereof may be a monounsaturated orpolyunsaturated carboxylic acid or derivative thereof with, for example,an alkene chain containing from 1 to about 4 carbon-carbon double bonds.The functionalized monomer may comprise or be derived from anunsaturated polyol ester, for example, an unsaturated monoglyceride, anunsaturated diglyceride, an unsaturated triglyceride, or a mixture oftwo or more thereof.

The functionalized monomer may comprise an olefin chain with 1, 2, 3 or4 carbon-carbon double bonds in the chain. The olefin chain may bederived from pentene, hexene, heptene, octene, nonene, decene, undecene,dodecene, tridecene, tetradecene, pentadecene, hexadecene, heptadecene,octadecene, or a mixture of two or more thereof. The olefin chain may bederived from octadiene, nonadiene, decadiene, undecadiene, dodecadiene,tridecadiene, tetradecadiene, pentadecadiene, tetradecatriene,pentadecatriene, hexadecatriene, heptadecatriene, octadecatriene,tetradecatetraene, pentadecatetraene, hexadecatetraene,heptadecatetraene, octadecatetraene, or a mixture of two or morethereof. The olefin chain may be derived from nonene, decene, dodecene,octadecene, or a mixture of two or more thereof, each of which may bealpha olefins.

The functionalized monomer may comprise an unsaturated fatty acid orunsaturated fatty ester. The unsaturated fatty ester may be an“unsaturated monoester” and/or an “unsaturated polyol ester”. Theunsaturated monoesters may comprise one or more unsaturated fatty acidsthat are esterified with one or more monofunctional alcohols. Thesealcohols may contain from 1 to about 20 carbon atoms, or from 1 to about12 carbon atoms, or from 1 to about 8 carbon atoms, or from 1 to about 4carbon atoms, and may include methanol, ethanol, propanol, butanol,mixtures of two or more thereof, and the like. The unsaturated polyolesters may comprise at least one unsaturated fatty acid that isesterified by the hydroxyl group of one or more polyols. The polyol maycontain from 2 to about 10 carbon atoms, and from 2 to about 6 hydroxylgroups. Examples may include ethylene glycol, glycerol,trimethylolpropane, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 2,3-butanediol, 2-ethyl-1,3-propanediol,2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, pentaerythritol, sorbitol, mixtures oftwo or more thereof, and the like.

The unsaturated fatty esters may be transesterified with one or morealcohols and/or polyols. For example, the unsaturated fatty ester maycomprise methyl 8-nonenoate, methyl 9-decenoate, methyl 10-undecenoate,methyl 9-dodecenoate, methyl 9-octadecenoate, or a mixture of two ormore thereof, which may be transesterified with one or more of thefollowing alcohols and/or a polyols. The alcohols may contain 2 to about20 carbon atoms, or from 2 to about 12 carbon atoms, or from 2 to about8 carbon atoms, or from 2 to about 4 carbon atoms, and may includeethanol, propanol, butanol, mixtures of two or more thereof, and thelike. The polyols may contain from 2 to about 10 carbon atoms, and from2 to about 6 hydroxyl groups. Examples may include ethylene glycol,glycerol, trimethylolpropane, 1,2-propanediol, 1,3-propanediol,1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-ethyl-1,3-propanediol,2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, pentaerythritol, sorbitol, mixtures oftwo or more thereof, and the like.

The unsaturated fatty acid and/or ester may have a straight alkene chainand may be represented by the formula:

CH₃—(CH₂)_(n1)—[—(CH₂)_(n3)—CH═CH—]_(x)—(CH₂)_(n2)—COOR

where:

-   -   R is hydrogen (fatty acid), or an aliphatic or aromatic group        (fatty ester);    -   n1 is an integer equal to or greater than 0 (typically 0 to        about 15; more typically 0, 3, or 6);    -   n2 is an integer equal to or greater than 0 (typically 1 to        about 11; more typically 3, 4, 7, 9, or 11);    -   n3 is an integer equal to or greater than 0 (typically 0 to        about 6; more typically 1); and    -   x is an integer equal to or greater than 1 (typically 1 to about        6, more typically 1 to about 3).

The unsaturated fatty acids and esters may include those provided in thefollowing table.

Unsaturated Fatty Acids/Esters

Examples Examples of fatty of fatty General Formula acids estersDiunsaturated Linoleic MethylCH₃—(CH₂)_(n1)—[—(CH₂)_(n3)—CH═CH—]_(x)—(CH₂)_(n2)—COOR acid LinoleateWhere x is 2, and n1, n2, n3, and R are as described (x = 2, n1 = (x =2, above. 3; n1 = 3; n2 = 7; n2 = 7; n3 = 1; n3 = 1; and R is and R isH.) CH3.) Triunsaturated Linolenic MethylCH₃—(CH₂)_(n1)—[—(CH₂)_(n3)—CH═CH—]_(x)—(CH₂)_(n2)—COOR acid LinolenateWhere x is 3, and n1, n2, n3, and R are as described (x = 3, n1 = (x =3, above. 0; n1 = 0; n2 = 7; n2 = 7; n3 = 1; n3 = 1; and R is and R isH.) CH3.)

Unsaturated monoesters may be alkyl esters (e.g., methyl esters) or arylesters and may be derived from unsaturated fatty acids or unsaturatedglycerides by transesterifying with a monohydric alcohol. The monohydricalcohol may be any monohydric alcohol that is capable of reacting withan unsaturated free fatty acid or unsaturated glyceride to form thecorresponding unsaturated monoester. The monohydric alcohol may be a C₁to C₂₀ monohydric alcohol, or a C₁ to C₁₂ monohydric alcohol, or a C₁ toC₈ monohydric alcohol, or a C₁ to C₄ monohydric alcohol. The carbonatoms of the monohydric alcohol may be arranged in a straight chain orin a branched chain structure, and may be substituted with one or moresubstituents. Representative examples of monohydric alcohols includemethanol, ethanol, propanol (e.g., isopropanol), butanol, mixtures oftwo or more thereof, and the like.

The functionalized monomer may comprise a transesterified unsaturatedtriglyceride. Transesterification of an unsaturated triglyceride may berepresented as follows.

1 Polyunsaturated Triglyceride+3 Alcohol→1 Glycerol+1-3 PolyunsaturatedMonoester

Depending upon the make-up of the polyunsaturated triglyceride, theabove reaction may yield one, two, or three moles of polyunsaturatedmonoester. Transesterification may be conducted in the presence of acatalyst, for example, alkali catalysts, acid catalysts, or enzymes.Representative alkali transesterification catalysts may include NaOH,KOH, sodium and potassium alkoxides (e.g., sodium methoxide), sodiumethoxide, sodium propoxide, sodium butoxide. Representative acidcatalysts may include sulfuric acid, phosphoric acid, hydrochloric acid,and sulfonic acids. Organic or inorganic heterogeneous catalysts mayalso be used for transesterification. Organic heterogeneous catalystsmay include sulfonic and fluorosulfonic acid-containing resins.Inorganic heterogeneous catalysts may include alkaline earth metals ortheir salts such as CaO, MgO, calcium acetate, barium acetate, naturalclays, zeolites, Sn, Ge or Pb, which may be supported on various supportmaterials such as ZnO, MgO, TiO₂, activated carbon or graphite,inorganic oxides such as alumina, silica-alumina, boria, and the like.The catalysts may comprise one or more of P, Ti, Zr, Cr, Zn, Mg, Ca, Fe,or an oxide thereof. The triglyceride may be transesterified withmethanol (CH₃OH) in order to form free fatty acid methyl esters.

The unsaturated fatty esters may comprise unsaturated polyol esters. Theunsaturated polyol ester compounds may have at least one unsaturatedfatty acid that is esterified by the hydroxyl group of a polyol. Theother hydroxyl groups of the polyol may be unreacted, may be esterifiedwith a saturated fatty acid, or may be esterified with a monounsaturatedfatty acid. Examples of polyols include glycerol and 1,3 propanediol, aswell as those mentioned above. The unsaturated polyol esters may havethe general formula:

R(O—Y)_(m)(OH)_(n)(O—X)_(b)

where

-   -   R is an organic group having a valency of (n+m+b);    -   m is an integer from 0 to (n+m+b−1), typically 0 to 2;    -   b is an integer from 1 to (n+m+b), typically 1 to 3;    -   n is an integer from 0 to (n+m+b−1), typically 0 to 2;    -   (n+m+b) is an integer that is 2 or greater;    -   X is —(O)C—(CH₂)_(n2)—[—CH═CH—(CH₂)_(n3)—]_(x)—(CH₂)_(n1)—CH₃;    -   Y is —(O)C—R′;    -   R′ is a straight or branched chain alkyl or alkenyl group;    -   n1 is an integer equal to or greater than 0 (typically 0 to 15;        more typically 0, 3, or 6);    -   n2 is an integer equal to or greater than 0 (typically 2 to 11;        more typically 3, 4, 7, 9, or 11);    -   n3 is an integer equal to or greater than 0 (typically 0 to 6;        more typically 1); and    -   x is an integer equal to or greater than 2 (typically 2 to 6,        more typically 2 to 3).

The unsaturated polyol esters may be unsaturated glycerides. The term“unsaturated glyceride” refers to a polyol ester having at least one(e.g., 1 to 3) unsaturated fatty acid that is esterified with a moleculeof glycerol. The fatty acid groups may be linear or branched and mayinclude pendant hydroxyl groups. The unsaturated glycerides may berepresented by the general formula:

CH₂A-CHB-CH₂C

-   -   where        -   -A; -B; and -C are selected from        -   —OH;        -   —O(O)C—(CH₂)_(n2)—[—CH═CH—(CH₂)_(n3)—]_(x)—(CH₂)_(n1)—CH₃;            and        -   —O(O)C—R′;    -   with the proviso that at least one of -A, -B, or -C is        -   —O(O)C—(CH₂)_(n2)—[—CH═CH—(CH₂)_(n3)—]_(x)—(CH₂)_(n1)—CH₃.    -   In the above formula:        -   R′ is a straight or branched chain alkyl or alkenyl group;        -   n1 is an integer equal to or greater than 0 (typically 0 to            15; more typically 0, 3, or 6);        -   n2 is an integer equal to or greater than 0 (typically 2 to            11; more typically 3, 4, 7, 9, or 11);        -   n3 is an integer equal to or greater than 0 (typically 0 to            6; more typically 1); and        -   x is an integer equal to or greater than 2 (typically 2 to            6, more typically 2 to 3).

Unsaturated glycerides having two —OH groups (e.g., -A and -B are —OH)may be referred to as unsaturated monoglycerides. Unsaturated glycerideshaving one —OH group may be referred to as unsaturated diglycerides.Unsaturated glycerides having no —OH groups may be referred to asunsaturated triglycerides.

The unsaturated glyceride may include monounsaturated fatty acids,polyunsaturated fatty acids, and saturated fatty acids that areesterified with the glycerol molecule. The main chain of the individualfatty acids may have the same or different chain lengths. Accordingly,the unsaturated glyceride may contain up to three different fatty acidsso long as at least one fatty acid is an unsaturated fatty acid.

The functionalized monomer may comprise a Δ9 polyunsaturated fatty acid,a Δ9 polyunsaturated fatty ester (e.g., monoesters or polyol esters), ora mixture thereof. Δ9 polyunsaturated fatty acids and/or esters may haveat least two carbon-carbon double bonds with one carbon-carbon doublebond being located between the 9^(th) and 10^(th) carbon atoms (i.e.,between C₉ and C₁₀) in the alkene chain of the polyunsaturated fattyacid and/or ester. In determining this position, the alkene chain isnumbered starting with the carbon atom of the carbonyl group of theunsaturated fatty acid and/or ester. Included within the definition ofΔ9 polyunsaturated fatty acids and/or esters are Δ9, Δ12 polyunsaturatedfatty acids and/or esters, and Δ9, Δ12, Δ15 polyunsaturated fatty acidsand/or esters.

The Δ9 polyunsaturated acid or ester may have a straight alkene chainand may be represented by the structure:

CH₃—(CH₂)_(n1)—[—(CH₂)_(n3)—CH═CH—]_(x)—(CH₂)₇—COOR

where

-   -   R is hydrogen (fatty acid), or an aliphatic group (fatty        monoester);    -   n1 is an integer equal to or greater than 0 (typically 0 to 6;        or 0, 3 or 6);    -   n3 is an integer equal to or greater than 0 (typically 1); and    -   x is an integer equal to or greater than 2 (typically 2 to 6,        more typically 2 to 3).

The Δ9 polyunsaturated fatty acid and/or ester may have a total of about12, 15 or 18 carbons in the alkene chain. Examples may include

CH₃—(CH₂)₄—CH═CH—CH₂—CH═CH—(CH₂)₇—COOR;

CH₃—CH₂—CH═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—COOR.

CH₂═CH—CH₂—CH═CH—(CH₂)₇—COOR; and

CH₂═CH—CH₂—CH═CH—CH₂—CH═CH—(CH₂)₇—COOR,

-   -   where R is hydrogen (fatty acid), or an aliphatic group (fatty        monoester);        Δ9 unsaturated fatty esters may be monoesters or polyol esters.        The Δ9 unsaturated polyol ester may have the general structure

CH₂A-CHB-CH₂C

-   -   where        -   -A; -B; and -C are independently selected from        -   —OH;        -   —O(O)C—R′; and        -   —O(O)C—(CH₂)₇—[—CH═CH—CH₂—]_(x)—(CH₂)_(n1)CH₃        -   with the proviso that at least one of -A, -B, or -C is        -   —O(O)C—(CH₂)₇—[—CH═CH—CH₂—]_(x)—(CH₂)_(n1)CH₃    -   In the above formula:        -   R′ is a straight or branched chain alkyl or alkenyl group;        -   n1 is independently an integer equal to or greater than 0            (typically 0 to 6); and        -   x is an integer greater than or equal to 2 (typically 2 to            6, more typically 2 to 3).

Δ9, Δ12 di-unsaturated esters and Δ9, Δ12, Δ15 tri-unsaturated estersmay be used.

The functionalized monomer may comprise one or more C₁₈ fatty acids, forexample, linoleic acid (i.e., 9,12-octadecadienoic acid) and linolenicacid (i.e., 9,12,15-octadecatrienoic acid). The functionalized monomermay comprise one or more C₁₈ fatty esters, for example, methyl linoleateand methyl linolenate. The functionalized monomer may comprise anunsaturated glyceride comprising Δ9 fatty acids, for example, C18:Δ9fatty acids.

Δ9, Δ12 and Δ15 functionalized monomers may be derived from vegetableoils such as soybean oil, rapeseed oil, corn oil, sesame oil, cottonseedoil, sunflower seed oil, canola oil, safflower oil, palm oil, palmkernel oil, linseed oil, castor oil, olive oil, peanut oil, corianderoil, almond oil, wheat germ oil, and the like. Since these vegetableoils yield predominately the glyceride form of the Δ9, Δ12 and Δ15unsaturated fatty esters, the oils may be processed (e.g., bytransesterification) to yield an unsaturated free fatty ester and/orunsaturated fatty acid. Δ9, Δ12 and Δ15 unsaturated fatty acids and/oresters, and salts may also be also be derived from tall oil, fish oil,lard, algal oil, poultry fat, yellow grease, and tallow. A summary ofsome useful functionalized monomers is provided in the following table.

Functionalized Monomer Description Classification Bond LocationsLinoleic acid C18 Δ9 Δ9, 12 diunsaturated fatty acid (C18:2) Linolenicacid C18 Δ9 Δ9, 12, 15 triunsaturated fatty acid (C18:3) Alkyl linoleateC18 Δ9 Δ9, 12 diunsaturated fatty ester (C18:2) Alkyl linolenate C18 Δ9Δ9, 12, 15 triunsaturated fatty ester (C18:3) Unsaturated Unsaturated Δ9Δ9 glyceride glycerides of Δ9, 12 C18:1, C18:2, Δ9, 12, 15 and C18:3fatty acids

The functionalized monomer may comprise an unsaturated carboxylic acidand/or ester used with an alkene chain of from about 10 to about 30carbon atoms, or from about 10 to about 24 carbon atoms, or about 18carbon atoms, and a carbon-carbon double bond between the C₉ and C₁₀carbon atoms in the alkene chain.

The functionalized monomer may comprise an unsaturated fatty acid and/orthe unsaturated fatty ester with an alkene chain of from 8 to about 30carbon atoms, or from about 8 to about 18 carbon atoms, or about 18carbon atoms, and a carbon-carbon double bond between the C₆ and C₇carbon atoms in the alkene chain.

The functionalized monomer may comprise an unsaturated fatty acid and/orunsaturated fatty ester with an alkene chain of about 14 to about 30carbon atoms, or from about 14 to about 18 carbon atoms, or about 18carbon atoms, and a carbon-carbon double bond between the C₁₂ and C₁₃carbon atoms in the alkene chain.

The functionalized monomer may comprise an unsaturated fatty acid and/orunsaturated fatty ester with an alkene chain of from about 16 to about30 carbon atoms, or from about 16 to about 18 carbon atoms, or about 18carbon atoms, and a carbon-carbon double bond between the C₁₅ and C₁₆carbon atoms in the alkene chain.

The functionalized monomer may comprise an unsaturated fatty acid and/orunsaturated fatty ester with an alkene chain of from 14 to about 30carbon atoms, or from about 14 to about 18 carbon atoms, or about 18carbon atoms, and carbon-carbon double bonds between the C₉ and C₁₀carbon atoms and between the C₁₂ and C₁₃ carbon atoms in the alkenechain.

The functionalized monomer may comprise an unsaturated fatty acid and/orunsaturated fatty ester with an alkene chain of from 16 to about 30carbon atoms, or from about 16 to about 18 carbon atoms, or about 18carbon atoms, with carbon-carbon double bonds between the C₉ and C₁₀carbon atoms, between the C₁₂ and C₁₃ carbon atoms, and between C₁₅ andC₁₆ carbon atoms in the alkene chain.

The functionalized monomer may comprise an unsaturated fatty acid and/orunsaturated fatty ester with an alkene chain from 16 to about 30 carbonatoms, or from about 16 to about 18 carbon atoms, or about 18 carbonatoms, and carbon-carbon double bonds between the C₆ and C₇ carbonatoms, between the C₉ and C₁₀ carbon atoms, between the C₁₂ and C₁₃carbon atoms, and between the C₁₅ and C₁₆ carbon atoms in the alkenechain.

The functionalized monomer may comprise 8-nonenoic acid, afunctionalized derivative of 8-nonenoic acid, or a combination thereof.The functionalized derivative of 8-nonenoic acid may comprise an ester.The ester may comprise 8-nonenoic acid methyl ester, 8-nonenoic acidethyl ester, 8-nonenoic acid n-propyl ester, 8-nonenoic acid iso-propylester, 8-nonenoic acid n-butyl ester, 8-nonenoic acid sec-butyl ester,8-nonenoic acid tert-butyl ester, 8-nonenoic acid neopentyl ester,8-nonenoic acid pentaerythritol ester, or a mixture of two or morethereof.

The functionalized monomer may comprise 9-decenoic acid, afunctionalized derivative of 9-decenoic acid, or a combination thereof.The functionalized derivative of 9-decenoic acid may comprise an ester.The ester may comprise 9-decenoic acid methyl ester, 9-decenoic acidethyl ester, 9-decenoic acid n-propyl ester, 9-decenoic acid iso-propylester, 9-decenoic acid n-butyl ester, 9-decenoic acid sec-butyl ester,9-decenoic acid tert-butyl ester, 9-decenoic acid neopentyl ester,9-decenoic acid pentaerythritol ester, or a mixture of two or morethereof. The functionalized monomer may comprise methyl 9-decenoate.

The functionalized monomer may, comprise 10-undecenoic acid, afunctionalized derivative of 10-undecenoic acid, and a combinationthereof. The functionalized derivative of 10-undecenoic acid maycomprise an ester. The ester may comprise 10-undecenoic acid methylester, 10-undecenoic acid ethyl ester, 10-undecenoic acid n-propylester, 10-undecenoic acid iso-propyl ester, 10-undecenoic acid n-butylester, 10-undecenoic acid sec-butyl ester, 10-undecenoic acid tert-butylester, 10-undecenoic acid neopentyl ester, 10-undecenoic acidpentaerythritol ester, or a mixture of two or more thereof.

The functionalized monomer may comprise 9-dodecenoic acid, afunctionalized derivative of 9-dodecenoic acid, or a combinationthereof. The functionalized derivative of 9-dodecenoic acid may comprisean ester. The ester may comprise 9-dodecenoic acid methyl ester,9-dodecenoic acid ethyl ester, 9-dodecenoic acid n-propyl ester,9-dodecenoic acid iso-propyl ester, 9-dodecenoic acid n-butyl ester,9-dodecenoic acid sec-butyl ester, 9-dodecenoic acid tert-butyl ester,9-dodecenoic acid neopentyl ester, 9-dodecenoic acid pentaerythritolester, or a mixture of two or more thereof.

The functionalized monomer may comprise 9-octadecenedioic acid, afunctionalized derivative of 9-octadecenedioic acid, or a combinationthereof. The functionalized derivative of 9-octadecenedioic acid maycomprise a mono- or a di-ester. The ester may comprise 9-octadecenedioicacid mono- or di-methyl ester, 9-octadecenedioic acid mono- or di-ethylester, 9-octadecenedioic acid mono- or di-n-propyl ester,9-octadecenedioic acid mono- or di-iso-propyl ester, 9-octadecenedioicacid mono- or di-n-butyl ester, 9-octadecenedioic acid mono- ordi-sec-butyl ester, 9-octadecenedioic acid mono- or di-tert-butyl ester,9-octadecenedioic acid mono- or di-neopentyl ester, 9-octadecenedioicacid mono- or di-pentaerythritol ester, or a mixture of two or morethereof.

The Metathesis Process

The functionalized monomer may comprise a metathesized natural oilderived unsaturated carboxylic acid and/or ester. The metathesizednatural oil derived unsaturated carboxylic acid and/or ester may beproduced using a self-metathesis process, a cross-metathesis process, ora combination thereof. The self-metathesis process may comprise reactinga natural oil or natural oil derived unsaturated carboxylic acid and/orester in the presence of a metathesis catalyst to form a metathesizednatural oil from which the metathesized natural oil derived unsaturatedcarboxylic acid and/or ester may be derived.

The cross-metathesis process may comprise reacting a natural oil ornatural oil derivative with another olefinic compound in the presence ofa metathesis catalyst to form the metathesized natural oil. The anotherolefinic compound may be a natural oil, a natural oil derivative or ashort chain olefin. The short chain olefin may comprise an alpha olefin,an internal olefin, or a mixture thereof. The internal olefin may besymmetric or asymmetric. The olefin may comprise one or more of ethene,propene, 2-butene, 3-hexene, 4-octene, 2-pentene, 2-hexene, 2-heptene,3-heptene, 2-octene, 3-octene, 2-nonene, 3-nonene, 4-nonene, ethylene,1-propene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene,1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-octadecene, 1-eicosene, or a mixture oftwo or more thereof.

Multiple, sequential metathesis reaction steps may be employed. Forexample, the metathesized natural oil or metathesized natural oilderived unsaturated carboxylic acid and/or ester may be made by reactinga natural oil or natural oil derived unsaturated carboxylic acid and/orester in the presence of a metathesis catalyst to form a firstmetathesized natural oil or first metathesized natural oil derivedunsaturated carboxylic acid and/or ester. The first metathesized naturaloil or first metathesized natural oil derived unsaturated carboxylicacid and/or ester may then be reacted in a self-metathesis reaction toform another metathesized natural oil or metathesized natural oilderived unsaturated carboxylic acid and/or ester. Alternatively, thefirst metathesized natural oil or metathesized natural oil derivedunsaturated carboxylic acid and/or ester may be reacted in across-metathesis reaction with a natural oil and/or natural oil derivedunsaturated carboxylic acid and/or ester to form another metathesizednatural oil or metathesized natural oil derived unsaturated carboxylicacid and/or ester. These procedures may be used to form metathesisdimers, trimers as well as higher order metathesis oligomers andpolymers. These procedures can be repeated as many times as desired (forexample, from 2 to about 50 times, or from 2 to about 30 times, or from2 to about 10 times, or from 2 to about 5 times, or from 2 to about 4times, or 2 or 3 times) to provide the desired metathesis oligomer orpolymer which may comprise, for example, from 2 to about 100 bondedgroups, or from 2 to about 50, or from 2 to about 30, or from 2 to about10, or from 2 to about 8, or from 2 to about 6 bonded groups, or from 2to about 4 bonded groups, or from 2 to about 3 bonded groups.

The metathesized natural oil or metathesized natural oil derivedunsaturated carboxylic acid and/or ester produced by the metathesisreaction process may comprise a mixture of carboxylic acids and/oresters, and olefins, comprising one or more metathesis monomers,oligomers and/or polymers derived from the unsaturates in the naturaloil. The number of bonded groups in the metathesized natural oilmonomers, oligomers or polymers may range from 1 to about 100, or from 2to about 50, or from 2 to about 30, or from 2 to about 10. These mayinclude metathesis monomers, metathesis dimers, metathesis trimers,metathesis tetramers, metathesis pentamers, and higher order metathesisoligomers or polymers (e.g., metathesis hexamers, heptamers, octamers,nonamers, decamers, and the like). These may be useful as thefunctionalized polymers or copolymers of the invention.

The metathesis starting materials or reactants may be subjected to ametathesis reaction to produce the desired metathesized product.Metathesis is a catalytic reaction that involves the interchange ofalkylidene units among compounds containing one or more double bonds(i.e., olefinic compounds) via the formation and cleavage of thecarbon-carbon double bonds. Metathesis can occur between two of the samemolecules (often referred to as self-metathesis) and/or it can occurbetween two different molecules (often referred to as cross-metathesis).

Self-metathesis may be represented generally as shown in Equation I.

R¹—HC═CH—R²+R¹—CH═CH—R²

R¹—CH═CH—R¹+R²—CH═CH—R²  (I)

-   -   where R¹ and R² are organic groups.        Cross-metathesis may be represented generally as shown in        Equation II.

R¹—HC═CH—R²+R³—HC═CH—R⁴

R¹—HC═CH—R³+R¹—HC═CH—R⁴+R²—HC═CH—R³+R²—HC═CH—R⁴+R¹—HC═CH—R¹+R²—HC═CH—R²+R³—HC═CH—R³+R⁴—HC═CH—R⁴  (II)

-   -   where R¹, R², R³, and R⁴ are organic groups.

When an unsaturated polyol ester comprises molecules having more thanone carbon-carbon double bond, self-metathesis may result inoligomerization or polymerization of the unsaturates in the startingmaterial. For example, reaction sequence (III) depicts metathesisoligomerization of a representative species (e.g., an unsaturated polyolester) having more than one carbon-carbon double bond. In reactionsequence (III), the self-metathesis reaction results in the formation ofmetathesis dimers, metathesis trimers, and metathesis tetramers.Although not shown, higher order oligomers such as metathesis pentamers,hexamers, heptamers, octamers, nonamers, decamers, and mixtures of twoor more thereof, may also be formed. The number of metathesis repeatingunits or groups in the metathesized oil may range from 1 to about 100,or from 2 to about 50, or from 2 to about 30, or from 2 to about 10, orfrom 2 to about 4. The molecular weight of the metathesis dimer may begreater than the molecular weight of the unsaturated polyol ester fromwhich the dimer is formed. Each of the bonded polyol ester molecules maybe referred to as a “repeating unit or group.” Typically, a metathesistrimer may be formed by the cross-metathesis of a metathesis dimer withan unsaturated polyol ester. Typically, a metathesis tetramer may beformed by the cross-metathesis of a metathesis trimer with anunsaturated polyol ester or formed by the cross-metathesis of twometathesis dimers.

R¹—HC═CH—R²—HC═CH—R³+R¹—HC═CH—R²—HC═CH—R³

R¹—HC═CH—R²—HC═CH—R²—HC═CH—R³+(other products)

(Metathesis Dimer)

R¹—R²—HC═CH—R²—HC═CH—R³+R¹—HC═CH—R²—HC═CH—R³

R¹—HC═CH—R²—HC═CH—R²—HC═CH—R²—HC═CH—R³+(other products)

(Metathesis Trimer)

R¹—HC═CH—R²—HC═CH—R²—HC═CH—R²—HC═CH—R³+R¹—HC═CH—R²—HC═CH—R³

R¹—HC═CH—R²—HC═CH—R²—HC═CH—R²—HC═CH—R²—HC═CH—R³+(other products)  (III)

(Metathesis Tetramer)

where R¹, R², and R³ are organic groups.

An unhydrogenated or partially hydrogenated polyol ester may besubjected to metathesis (self or cross). An exemplary self-metathesisreaction scheme is shown in FIG. 1. The reaction scheme shown in FIG. 1highlights the reaction of the major fatty acid group component of thehydrogenation product composition (i.e., triacylglycerides having amonounsaturated fatty acid group). As shown in FIG. 1, a triglyceridehaving a monounsaturated fatty acid group is self-metathesized in thepresence of a metathesis catalyst to form a metathesis productcomposition. Within FIG. 1, the R group designates a diglyceride. InFIG. 1, the reactant composition A comprises triglyceride having amonounsaturated fatty acid group. The resulting metathesized productcomposition includes, as major components, monounsaturated diacid estersin triglyceride form B, internal olefins C and monounsaturated fattyacid esters in triglyceride form D. Any one or more of the startingmaterial A and each of the products shown, B, C and D, may be present asthe cis or trans isomer. Unreacted starting material may also be present(not shown). As illustrated, the metathesized products, B, C and D mayhave overlapping chain lengths.

A concern when performing metathesis of natural oils in theirtriglyceride or other form may be the generation light co-products.Naturally occurring methylene interrupted cis, cis configuration mayform cyclic compounds that may be present as volatile organic compounds(VOCs). Depending upon the identity and amount of the VOC, it mayrepresent a yield loss and/or a hazardous emission. It may thus bedesirable to reduce the formation of VOCs during the metathesisreaction. As the concentration of polyunsaturates is reduced, this inturn reduces the likelihood of generating such metathesis products ascyclohexadienes (e.g., 1,3-cyclohexadiene, 1,4-cyclohexadiene, and thelike), which themselves can be VOCs and/or be converted to other VOCs,such as benzene. Thus, in some aspects, the metathesis process mayreduce the generation of VOCs and/or control the identity of any yieldloss that can result from the metathesis reaction.

In some aspects, then, the invention can provide methods wherein theoccurrence of methylene interrupted cis-cis diene structures may bereduced in the metathesis reaction mixture. These structures may beconverted to other structures by geometric isomerization, positionalisomerization, and/or hydrogenation. In turn, these methods may reducevolatile co-product formation, e.g., in the form of cyclohexadiene.

An exemplary cross-metathesis reaction scheme is illustrated in FIG. 2.As shown in FIG. 2, a triglyceride having a monounsaturated fatty acidgroup is cross-metathesized with a short chain olefin (ethylene shown infigure), in the presence of a metathesis catalyst to form a metathesisproduct composition. The short chain olefins may include, for example,ethylene, propylene, 1-butene, 2-butene, isobutene, 1-pentene,2-pentene, isopentene, 2-hexene, 3-hexene, and the like.

As shown in FIG. 2, the reactant composition E includes triglyceridehaving a monounsaturated fatty acid group and ethylene. The resultingmetathesized product composition includes, as major components,monounsaturated fatty acid esters in triglyceride form having terminaldouble bonds F, as well as olefins with terminal double bonds G.Unreacted starting material can also be present, as well as productsfrom some amount of self-metathesis (not shown in figure). The startingmaterial and each of the products shown, E and F, may be present as thecis or trans isomer (except when ethylene is used in which case theproduct is a terminal olefin). As illustrated, the metathesizedproducts, E and F, may have overlapping chain lengths. The chain lengthsof the terminal monounsaturated fatty acid esters may be in the rangefrom about 5 to about 17 carbons. In some aspects, the majority (e.g.,50% or more) of the terminal monounsaturated fatty acids may have chainlengths in the range of from about 9 to about 13 carbon atoms.

The metathesis process can be conducted under any conditions adequate toproduce the desired metathesis products. For example, stoichiometry,atmosphere, solvent, temperature and pressure can be selected to producea desired product and to minimize undesirable byproducts. The metathesisprocess may be conducted under an inert atmosphere. Similarly, if theolefin reagent is supplied as a gas, an inert gaseous diluent can beused. The inert atmosphere or inert gaseous diluent typically is aninert gas, meaning that the gas does not interact with the metathesiscatalyst to substantially impede catalysis. For example, particularinert gases are selected from the group consisting of helium, neon,argon, nitrogen and combinations thereof.

Similarly, if a solvent is used, the solvent chosen may be selected tobe substantially inert with respect to the metathesis catalyst. Forexample, substantially inert solvents include, without limitation,aromatic hydrocarbons, such as benzene, toluene, xylenes, etc.;halogenated aromatic hydrocarbons, such as chlorobenzene anddichlorobenzene; aliphatic solvents, including pentane, hexane, heptane,cyclohexane, etc.; and chlorinated alkanes, such as dichloromethane,chloroform, dichloroethane, etc.

In certain embodiments, a ligand may be added to the metathesis reactionmixture. In many embodiments using a ligand, the ligand is selected tobe a molecule that stabilizes the catalyst, and may thus provide anincreased turnover number for the catalyst. In some cases the ligand canalter reaction selectivity and product distribution. Examples of ligandsthat can be used include Lewis base ligands, such as, withoutlimitation, trialkylphosphines, for example tricyclohexylphosphine andtributyl phosphine; triarylphosphines, such as triphenylphosphine;diarylalkylphosphines, such as, diphenylcyclohexylphosphine; pyridines,such as 2,6-dimethylpyridine, 2,4,6-trimethylpyridine; as well as otherLewis basic ligands, such as phosphine oxides and phosphinites.Additives may also be present during metathesis that increase-catalystlifetime.

Any useful amount of the selected metathesis catalyst can be used in theprocess. For example, the molar ratio of the unsaturated polyol ester tocatalyst may range from about 5:1 to about 10,000,000:1, or from about50:1 to 500,000:1.

The metathesis reaction temperature may be a rate-controlling variablewhere the temperature is selected to provide a desired product at anacceptable rate. The metathesis temperature may be greater than −40° C.,may be greater than about −20° C., and is typically greater than about0° C. or greater than about 20° C. Typically, the metathesis reactiontemperature is less than about 150° C., typically less than about 120°C. An exemplary temperature range for the metathesis reaction may rangefrom about 20° C. to about 120° C.

The metathesis reaction can be run under any desired pressure.Typically, it will be desirable to maintain a total pressure that ishigh enough to keep the cross-metathesis reagent in solution. Therefore,as the molecular weight of the cross-metathesis reagent increases, thelower pressure range typically decreases since the boiling point of thecross-metathesis reagent increases. The total pressure may be selectedto be greater than about 10 kPa, in some embodiments greater than about30 kPa, or greater than about 100 kPa. Typically, the reaction pressureis no more than about 7000 kPa, in some embodiments no more than about3000 kPa. An exemplary pressure range for the metathesis reaction isfrom about 100 kPa to about 3000 kPa. In some embodiments, it may bedesirable to conduct self-metathesis under vacuum conditions, forexample, at low as about 0.1 kPa.

The metathesis reaction may be used to convert triglycerides havingrelatively long-chain fatty acid esters (e.g., C₁₆-C₂₂) to a productmixture comprising: linear alpha-olefins (e.g., C₆-C₁₂ alpha-olefins),for example, 1-octene, 1-decene, 1-dodecene, and the like; internalolefins (e.g., C₁₆-C₂₂ internal olefins), for example, 9-octadecene;di-olefins, for example, 1,4-octadiene, 1,4-decadiene, 1,4-dodecadiene,and the like; and reduced chain length triglycerides (e.g., C₈-C₁₄). Thereaction may be a cross-metathesis reaction wherein the triglyceride andan olefin (e.g., ethylene, propylene, butene, etc.) are reacted in thepresence of a metathesis catalyst to produce the desired product mix.The product mix may be referred to as a metathesized triglyceride.

A process for metathesizing a natural and treating the resultingmetathesized natural oil is illustrated in FIG. 3. In this process, themetathesized natural oil is separated into olefins, and carboxylic acidsand/or esters which may then undergo subsequent treatment. Referring toFIG. 3, natural oil reactant 12 may be reacted with itself, oroptionally with another olefinic compound 14, in metathesis reactor 20in the presence of a metathesis catalyst. The natural oil reactant 12may undergo a self-metathesis reaction, or it may undergo across-metathesis reaction with the another olefinic compound 14. Thenatural oil reactant 12 may undergo both self- and cross-metathesisreactions in separate metathesis reactors. Multiple parallel orsequential metathesis reactions may be conducted. The self-metathesisand/or cross-metathesis reactions may be used to form a metathesizednatural oil product 22. The metathesized natural oil product 22 maycomprise one or more olefins 32 (e.g., 1-decene) and one or morecarboxylic acids and/or esters (e.g., methyl 9-decenoate). Themetathesized natural oil product 22 may undergo a separation process inseparation unit 30 to form olefin stream 32, and carboxylic acid and/orester stream 34. Separation unit 30 may comprise a distillation unit.

The olefins from 32 and/or olefins from downstream of 32 (e.g., 42,etc.) may be used as a source of olefin comonomers in forming thefunctionalized copolymer of the present invention. The carboxylic acidsand/or esters from 34 and/or from downstream of 34 (e.g., 72, etc.) maybe used as a source of the functionalized monomers of the presentinvention.

The use of branched short chained olefins in the metathesis reaction mayprovide for the formation of a metathesized natural oil product withbranched olefins. These may be subsequently hydrogenated to formiso-paraffins. The branched short chain olefins may be useful forproviding desired performance properties for middle distillate fuelssuch as jet fuels, kerosene, diesel fuel, and the like.

It may be possible to use a mixture of various linear or branched shortchain olefins in the metathesis reaction to achieve a desired productdistribution. For example, a mixture of butenes (e.g., 1-butene,2-butene, and, optionally, isobutene) may be employed as the anotherolefinic compound. This may allow for the use of a low cost,commercially available feedstock instead of a purified source of oneparticular butene. These low cost butene feedstocks may be diluted withn-butane and/or isobutane.

Recycled streams from downstream separation units may be combined withthe reactant 12 and, optionally, the another olefinic compound 14, inthe metathesis reactor 20. For example, a low molecular weight (e.g.,C₂-C₆) olefin stream 44 and bottoms (e.g., C₁₅+) olefin stream 46 fromseparation unit 40 may be recycled to the metathesis reactor 20.

The metathesized natural oil product 22 may flow through a flash vesselor flash drum (not shown in FIG. 3) operated under temperature andpressure conditions that may be used to target C₂ or C₂-C₃ olefincompounds as light ends. These compounds may be flashed off and removed.The light ends may be sent to another separation unit (now shown in FIG.3), where the C₂ or C₂-C₃ olefin compounds may be further separated fromhigher molecular weight or heavier compounds that may have flashed offwith the C₂ or C₂-C₃ olefin compounds. The heavier compounds maycomprise, for example, C₃-C₅ olefin compounds. After separation, the C₂or C₂-C₃ olefins may be used as the olefin comonomer of the presentinvention. Alternatively, these olefins may be used for otherapplications or as a fuel source. The bottoms stream from the flashvessel or flash drum may contain mostly C₃-C₅ olefin compounds which maybe used as the olefin comonomer of the present invention, returned as arecycle stream to the metathesis reactor 20, or separated from theprocess and used for other applications or as a fuel source. Themetathesized natural oil product 22 that does not flash in the flashvessel or flash drum may be advanced downstream to separation unit 30.

The metathesized natural oil product 22 may be treated in an adsorbentbed to facilitate the separation of the metathesized natural oil product22 from the metathesis catalyst prior to entering the flash vessel ordrum and/or prior to entering separation unit 30. The adsorbent maycomprise a clay bed. The clay bed may adsorb the metathesis catalyst.After a filtration step, the metathesized natural oil product 22 may besent to the flash vessel or flash drum and/or to the separation unit 30.Alternatively, the adsorbent may comprise a water soluble phosphinereagent such as trishydroxymethyl phosphine (THMP). The catalyst may beseparated using the water soluble phosphine via liquid-liquidextraction. Alternatively, the metathesized natural oil product 22 maybe reacted with a reagent to deactivate or to extract the catalyst.

In the separation unit 30, the metathesized natural oil product 22 maybe separated into two or more product streams, these product streamscomprising olefin stream 32, and carboxylic acid and/or ester stream 34.In an embodiment, a byproduct stream comprising desired olefins, and/oracids and/or esters may be removed in a side-stream from the separationunit 30. The separated olefins 32 may comprise hydrocarbons with carbonnumbers up to, for example, about 24, or higher. The carboxylic acidsand/or esters 34 may comprise one or more triglycerides. The olefins 32may be separated or distilled overhead for processing into olefincompositions, while the carboxylic acids and/or esters 34 may be drawninto a bottoms stream. Based on the quality of the separation, it ispossible for some lighter acids and/or esters to be carried into theolefin stream 32, and it is also possible for some heavier olefins to becarried into the acid and/or ester stream 34.

The olefins 32 may be collected and sold for any number of known usesand/or used as a source of the olefin comonomers in accordance with thepresent invention. The olefins 32 may be further processed in an olefinseparation unit 40 and/or in separation unit 60.

The carboxylic acids and/or esters 34 may comprise one or moreunsaturated carboxylic acids, and/or one or more unsaturated carboxylicesters. These may include glycerides and free fatty acids. The acidsand/or esters 34 may be separated or distilled for further processinginto various products and/or used as a source of functionalized monomersin accordance with the present invention. In an embodiment, furtherprocessing may target, for example, C₅-C₁₈ fatty acids and/or C₅-C₁₈fatty acid esters. These may include fatty acid methyl esters, such as9-decenoic acid (9DA) esters, 10-undecenoic acid (10UDA) esters,9-dodecenoic acid (9DDA) esters and/or 9-octadecenoic (9DDA) esters;9DA, 10UDA, 9DDA and/or 9DDA; and/or diesters of transesterifiedproducts; or mixtures of two or more thereof. Further processing maytarget, for example, the production of diacids, anhydrides, diesters,amides, imides, and the like. These may be used as the functionalizedmonomers in accordance with the present invention.

The olefins 32 may be further separated or distilled in the olefinseparation unit 40. Light end olefins, which may comprise, for example,C₂-C₉ olefins, or C₃-C₈ olefins, may be distilled into an overheadstream 44. Heavier olefins (e.g., C₁₆+ olefins) in olefin bottoms stream46 may be combined with the light end olefin stream 44 to assist intargeting a specific monomer composition. The light end olefins 44 maybe recycled to the metathesis reactor 20 and/or purged from the systemfor further processing. The light end olefins 44 may be partially purgedfrom the system and partially recycled to the metathesis reactor 20. Theolefin bottoms stream 46 may be purged and/or recycled to the metathesisreactor 20 for further processing. The light end olefins 44 and/orolefin bottoms stream 46 may be used as the olefin comonomers of thepresent invention. A center-cut olefin stream 42 may be separated in theolefin distillation unit 40 and subjected to further processing. Thecenter-cut olefins 42 may be used to target a selected olefindistribution for a specific end use. For example, the center cut stream42 may comprise a C₆-C₂₄ olefin distribution which may be used as theolefin comonomers in accordance with the present invention. A C₅-C₁₅olefin distribution may be targeted for further processing as anaphtha-type jet fuel. A C₈-C₁₆ distribution may be targeted for furtherprocessing into a kerosene-type jet fuel. A C₈-C₂₅ distribution may betargeted for further processing into a diesel fuel.

The olefins 32, 42, 44 and/or 46 may be oligomerized or polymerized toform poly-alpha-olefins (PAOs) and/or poly-internal-olefins (PIOs). Theoligomerization or polymerization reaction may be conducted downstreamof the separation unit 30 or downstream of the separation unit 40.Byproducts from the oligomerization or polymerization reactions may berecycled back to the metathesis reactor 20 for further processing.

The carboxylic acids and/or esters 34 from the separation unit 30 may bewithdrawn as product stream 36 and processed further or sold for theirown value. These acids and/or esters may be used as the functionalizedmonomers in accordance with the present invention. Based upon thequality of separation between olefins 32 and acids and/or esters 34, theacid and/or esters 34 may contain some heavier olefin components carriedover with the functionalized olefins. The acids and/or esters 34 may bepolymerized, copolymerized or functionalized in accordance with theinvention. The acids and/or esters 34 may be further processed in abiorefinery or another chemical or fuel processing unit, therebyproducing various products such as biofuels (e.g., biodiesel) orspecialty chemicals. The acids and/or esters 34 may be partiallywithdrawn from the system and sold, with the remainder further processedin the biorefinery or chemical or fuel processing unit.

The carboxylic acid and/or ester stream 34 may be advanced totransesterification unit 70. In the transesterification unit 70, theesters may be transesterified with one or more alcohols 38 in thepresence of a transesterification catalyst. The alcohol may comprisemethanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol,octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol,isopropanol, isobutanol, sec-butanol, tert-butanol, isopentanol, amylalcohol, tert-pentanol, cyclopentanol, cyclohexanol, allyl alcohol,crotyl alcohol, methylvinyl carbinol, benzyl alcohol, alpha-phenylethylalcohol, beta-phenylethyl alcohol, diphenylcarbinol, triphenylcarbinol,cinnamyl alcohol, or a mixture of two or more thereof. Thetransesterification reaction may be conducted at any suitabletemperature, for example, in the range from about 60 to about 70° C.,and at a suitable pressure, for example, atmospheric pressure. Thetransesterification catalyst may comprise a homogeneous sodium methoxidecatalyst. Varying amounts of catalyst may be used in the reaction. Thetransesterification catalyst may be used at a concentration of about 0.5to about 1% by weight based on the weight of the esters.

The transesterification reaction may be used to produce transesterifiedproducts 72, which may include saturated and/or unsaturated fatty acidmethyl esters (FAME), glycerin, methanol, and/or free fatty acids. Thetransesterified products 72, or a fraction thereof, may be used as amiddle distillate fuel such as biodiesel. The transesterified products72 may comprise 9-decenoic acid (9DA) esters, 10-undecenoic acid (10UDA)esters, 9-dodecenoic acid (9DDA) esters, and/or 9-octadecenoic acid(9ODDA) esters. Examples of the 9DA esters, 10UDA esters, 9DDA esters,and 9ODDA esters may include methyl 9-decenoate (“9-DAME”), methyl10-undecenoate (“10-UDAME”), methyl 9-dodecenoate (“9-DDAME”), methyl9-octadecenoate (“9-ODDAME”), respectively. The esters may includeethyl-, n-propyl-, isopropyl-, n-butyl-, sec-butyl-, tert-butyl- and/orpentaerythritol esters of 9DA, 10UDA, 9DDA and/or 9ODDA, mixtures of twoor more thereof, and the like. In the transesterification reaction, a9DA moiety of a metathesized glyceride may be removed from the glycerolbackbone to form a 9DA ester.

In an embodiment, glycerol may be used in the transesterificationreaction with a glyceride stream. This reaction may be used to producemonoglycerides and/or diglycerides.

The transesterified products 72 from the transesterification unit 70 maybe advanced to a liquid-liquid separation unit, wherein thetransesterified products 72 (e.g., fatty acid esters, free fatty acids,and/or alcohols) may be separated from glycerin. In an embodiment, theglycerin byproduct stream may be further processed in a secondaryseparation unit, wherein the glycerin may be removed and any remainingalcohols may be recycled back to the transesterification unit 70 forfurther processing.

In an embodiment; the transesterified products 72 may be furtherprocessed in a water-washing unit. In this unit, the transesterifiedproducts may undergo a liquid-liquid extraction when washed with water.Excess alcohol, water, and glycerin may be removed from thetransesterified products 72. In another embodiment, the water-washingstep may be followed by a drying unit in which excess water may beremoved from the desired mixture of esters which may be used asspecialty chemicals. These specialty chemicals may include, for example,esters of 9DA, 10UDA, 9DDA and/or 9ODDA.

The transesterified products 72 from the transesterification unit 70 orspecialty chemicals from the water-washing unit or drying unit may beadvanced to ester distillation column 80 for further separation ofvarious individual or groups of compounds. This separation may be usedto provide for the separation of 9DA esters, 10UDA esters, 9DDA estersand/or 9ODDA esters. In an embodiment, 9DA ester 82 may be distilled orindividually separated from the remaining mixture 84 of transesterifiedproducts or specialty chemicals. The 9DA ester 82 may be the lightestcomponent in the transesterified product or specialty chemical stream,and may come out at the top of the ester distillation column 80. In anembodiment, the remaining mixture 84, or heavier components, of thetransesterified products or specialty chemicals may be separated at thebottom end of the distillation column 80. This bottoms stream 84 may beused as a middle distillate fuel such as biodiesel.

The 9DA esters, 10UDA esters, 9DDA esters and/or 9ODDA esters may befurther processed after the distillation step in the ester distillationcolumn 80 and/or used as a source of the functionalized monomer inaccordance with the present invention. In an embodiment, the 9DA ester,10UDA ester, 9DDA ester and/or 9ODDA may undergo a hydrolysis reactionwith water to form 9DA, 10UDA, 9DDA and/or 9ODDA.

In an embodiment, the fatty acid esters from the transesterifiedproducts 72 may be reacted with each other to form other specialtychemicals such as dimers.

Hydrogenation

The natural oil and/or natural oil derived unsaturated carboxylic acidand/or ester may be partially hydrogenated prior to undergoing achemical reaction (e.g., a metathesis reaction). Also, thefunctionalized monomer and/or functionalized polymer derived from thefunctionalized monomer may be partially or fully hydrogenated toaccommodate end use requirements.

Multiple unsaturated bonds within a polyunsaturated reactant providemultiple reaction sites. Multiple reaction sites may exponentiallyincrease the chemical identity of the reaction products, which in turnmay increase the complexity of the product composition. Multiplereaction sites within the reactants may also increase catalyst demandfor the reaction. These factors may increase the overall complexity andinefficiency of the reaction process.

More efficient reaction processes that can reduce catalyst demand andreduce complexity of the reaction product compositions may be providedby partially hydrogenating polyunsaturated reactants in the startingmaterial prior to conducting the reaction process. The partiallyhydrogenated reactant may then be subjected to the desired reactionprocess (e.g., a metathesis reaction process) to provide a desiredproduct.

The fatty esters may be hydrolyzed to yield linear fatty acids havingterminal carbon-carbon double bonds. In some embodiments, the linearfatty acids with terminal carbon-carbon double bonds aremonounsaturated. In some embodiments, the terminal linear fatty acidshave a chain length in the range of 3 to n carbon atoms (where n is thechain length of the partially hydrogenated composition which has adouble bond at the 2 to (n−1) position after partial hydrogenation). Inother embodiments, the terminal fatty acids have a chain length in therange of 5 to (n−1) carbon atoms (where n is the chain length of thepartially hydrogenated composition which has a double bond at the 4 to(n−2) position after partial hydrogenation). In exemplary embodiments,the terminal fatty acids have a chain length in the range of about 5 toabout 17 carbon atoms. In other aspects, the reaction (e.g., metathesisreaction) products are monounsaturated diesters having a chain length inthe range of about 4 to (2n−2) carbon atoms (where n is the chain lengthof the partially hydrogenated composition, which has a double bond atthe 2 to (n−1) position after partial hydrogenation). In otherembodiments, the monounsaturated diesters have a chain length in therange of about 8 to (2n−4) carbon atoms (where n is the chain length ofthe partially hydrogenated composition which has a double bond at the 4to (n−2) position after partial hydrogenation). In exemplaryembodiments, the monounsaturated diesters may have a chain length in therange of about 8 to about 32 carbon atoms.

The polyunsaturated starting materials may be partially hydrogenatedunder conditions to optimize the starting composition for the chemicalreactions. Partial hydrogenation may be used to reduce the number ofdouble bonds that are available to participate in the reaction.

Partial hydrogenation can also alter the fatty acid composition of thepolyunsaturated fatty acid starting materials or reactants. Positionaland/or geometrical isomerization can occur during hydrogenation, thuschanging the location and/or orientation of the double bonds. Thesereactions may occur concurrently. In the geometrical isomers, the cisbonds originally present in naturally occurring soybean oil may beconverted in part to the trans form.

Partial hydrogenation can be conducted according to any known method forhydrogenating double bond-containing compounds such as vegetable oils.Catalysts for hydrogenation are known and can be homogeneous orheterogeneous (e.g., present in a different phase, typically the solidphase, than the substrate). A useful hydrogenation catalyst is nickel.Other useful hydrogenation catalysts include copper, palladium,platinum, molybdenum, iron, ruthenium, osmium, rhodium, iridium, zinc orcobalt. Combinations of catalysts can also be used. Bimetallic catalystscan be used, for example, palladium-copper, palladium-lead,nickel-chromite.

The metal catalysts can be utilized with promoters that may or may notbe other metals. Illustrative metal catalysts with promoter include, forexample, nickel with sulfur or copper as promoter; copper with chromiumor zinc as promoter; zinc with chromium as promoter; or palladium oncarbon with silver or bismuth as promoter.

The polyunsaturated starting composition may be partially hydrogenatedin the presence of a nickel catalyst that has been chemically reducedwith hydrogen to an active state. Commercial examples of supportednickel hydrogenation catalysts may include those available under thetrade designations “NYSOFACT,” “NYSOSEL,” and “NI 5248 D” (fromEngelhard Corporation, Iselin, N.J.). Additional supported nickelhydrogenation catalysts may include those commercially available underthe trade designations “PRICAT 9910,” “PRICAT 9920,” “PRICAT 9908” and“PRICAT 9936” (from Johnson Matthey Catalysts, Ward Hill, Mass.).

The metal catalysts can be in the form of fine dispersions in ahydrogenation reaction (slurry phase environment). For example, in someembodiments, the particles of supported nickel catalyst may be dispersedin a protective medium comprising hardened triacylglyceride, edible oil,or tallow. In an exemplary embodiment, the supported nickel catalyst maybe dispersed in the protective medium at a level of about 22 wt %nickel.

The catalysts may be impregnated on solid supports. Some useful supportsinclude carbon, silica, alumina, magnesia, titania, and zirconia, forexample. Illustrative support embodiments include, for example,palladium, platinum, rhodium or ruthenium on carbon or alumina support;nickel on magnesia, alumina or zirconia support; palladium on bariumsulfate (BaSO₄) support; or copper on silica support.

The catalysts may be supported nickel or sponge nickel type catalysts.The hydrogenation catalyst may comprise nickel that has been chemicallyreduced with hydrogen to an active state (i.e., reduced nickel) providedon a support. The support may comprise porous silica (e.g., kieselguhr,infusorial, diatomaceous, or siliceous earth) or alumina. The catalystsmay be characterized by a high nickel surface area per gram of nickel.

The supported nickel catalysts may be of the type reported in U.S. Pat.No. 3,351,566. These catalysts comprise solid nickel-silica having astabilized high nickel surface area of 45 to 60 sq. meters per gram anda total surface area of 225 to 300 sq. meters per gram. The catalystsare prepared by precipitating the nickel and silicate ions from solutionsuch as nickel hydrosilicate onto porous silica particles in suchproportions that the activated catalyst contains 25 wt % to 50 wt %nickel and a total silica content of 30 wt % to 90 wt %. The particlesare activated by calcining in air at 600° F. to 900° F. (315.5° C. to482.2° C.), then reducing with hydrogen.

Useful catalysts having a high nickel content may include thosedescribed in EP 0 168 091. A soluble aluminum compound may be added tothe slurry of the precipitated nickel compound while the precipitate ismaturing. After reduction of the resultant catalyst precursor, thereduced catalyst typically has a nickel surface area on the order of 90to 150 sq. meters per gram of total nickel. The catalysts may have anickel/aluminum atomic ratio in the range of 2 to 10 and have a totalnickel content of more than about 66% by weight.

Useful high activity nickel/alumina/silica catalysts may include thosedescribed in EP 0 167 201. The reduced catalysts may have a high nickelsurface area per gram of total nickel in the catalyst.

Useful nickel/silica hydrogenation catalysts may include those describedin U.S. Pat. No. 6,846,772. The catalysts may be produced by heating aslurry of particulate silica (e.g., kieselguhr) in an aqueous nickelamine carbonate solution for a total period of at least 200 minutes at apH above 7.5, followed by filtration, washing, drying, and optionallycalcination. The nickel/silica hydrogenation catalysts are reported tohave improved filtration properties. U.S. Pat. No. 4,490,480 reportshigh surface area nickel/alumina hydrogenation catalysts having a totalnickel content of 5% to 40% by weight.

The amount of hydrogenation catalysts may be selected in view of anumber of factors including, for example, the type of hydrogenationcatalyst(s) used, the degree of unsaturation in the material to behydrogenated, the desired rate of hydrogenation, the desired degree ofhydrogenation (for example, as measured by the IV, see below), thepurity of the reagent and the H₂ gas pressure. The hydrogenationcatalyst may be used in an amount of about 10 wt % or less, for exampleabout 5 wt % or less, about 1 wt % or less, or about 0.5 wt % or less.

Hydrogenation may be carried out in a batch, continuous orsemi-continuous process. In a representative batch process, a vacuum ispulled on the headspace of a stirred reaction vessel and the reactionvessel is charged with the material to be hydrogenated (for example, RBDsoybean oil). The material is then heated to a desired temperature,typically in the range of about 50° C. to about 350° C., or about 100°C. to about 300° C., or about 150° C. to about 250° C. The desiredtemperature can vary, for example, with hydrogen gas pressure.Typically, a higher gas pressure will require a lower temperature. In aseparate container, the hydrogenation catalyst is weighed into a mixingvessel and is slurried in a small amount of the material to behydrogenated (for example, RBD soybean oil). When the material to behydrogenated reaches the desired temperature (typically a temperaturebelow a target hydrogenation temperature), the slurry of hydrogenationcatalyst may be added to the reaction vessel. Hydrogen may then bepumped into the reaction vessel to achieve a desired pressure of H₂ gas.Typically, the H₂ gas pressure ranges from about 15 psig (103.4kilopascals) to about 3000 psig (20684.3 kilopascals), for example,about 15 psig (103.4 kilopascals) to about 90 psig (620.5 kilopascals).As the gas pressure increases, more specialized high-pressure processingequipment can be required. Under these conditions the hydrogenationreaction may begin and the temperature may be allowed to increase to thedesired hydrogenation temperature (for example, about 120° C. to about200° C.), where it may be maintained by cooling the reaction mass, forexample, with cooling coils. When the desired degree of hydrogenationhas been reached, the reaction mass may be cooled to the desiredfiltration temperature.

The polyunsaturated starting materials or reactants may be subjected toelectrocatalytic hydrogenation to achieve a partially hydrogenatedproduct. Various electrocatalytic hydrogenation processes can beutilized. For example, low temperature electrocatalytic hydrogenationthat uses an electrically conducting catalyst such as Raney Nickel orPlatinum black as a cathode are described in Yusem and Pintauro, J.Appl. Electrochem. 1997, 27, 1157-71. Another system that utilizes asolid polymer electrolyte reactor composed of a ruthenium oxide (RuO₂)powder anode and a platinum-black (Pt-black) or palladium-black(Pd-black) powder cathode that are hot-pressed as thin films onto aNafion cation exchange membrane is described in An et al. J. Am. OilChem. Soc. 1998, 75, 917-25. A further system that involveselectrochemical hydrogenation using a hydrogen transfer agent of formicacid and a nickel catalyst is described in Mondal and Lalvani, J. Am.Oil Chem. Soc. 2003, 80, 1135-41.

Hydrogenation may be performed under supercritical fluid state, asdescribed in U.S. Pat. Nos. 5,962,711 and 6,265,596.

Hydrogenation may be conducted in a manner to promote selectivity towardmonounsaturated fatty acid groups, i.e., fatty acid groups containing asingle carbon-carbon double bond. Selectivity is understood here as thetendency of the hydrogenation process to hydrogenate polyunsaturatedfatty acid groups over monounsaturated fatty acid groups. This form ofselectivity is often called preferential selectivity, or selectivehydrogenation.

The level of selectivity of hydrogenation may be influenced by thenature of the catalyst, the reaction conditions, and the presence ofimpurities. Generally speaking, catalysts having a high selectivity forone fat or oil reactant may also have a high selectivity in other fat oroil reactants. As used herein, “selective hydrogenation” refers tohydrogenation conditions (e.g., selection of catalyst, reactionconditions such as temperature, rate of heating and/or cooling, catalystconcentration, hydrogen availability, and the like) that are chosen topromote hydrogenation of polyunsaturated compounds to monounsaturatedcompounds. Using soybean oil as an example, the selectivity of thehydrogenation process may be determined by examining the content of thevarious C₁₈ fatty acids and their ratios. Hydrogenation on a macro scalemay be regarded as a stepwise process:

The following selectivity ratios (SR) may be defined: SRI=k₂/k₃;SRII=k₃/k₂; SRIII=k₂/k₁. Characteristics of the starting oil and thehydrogenated product may be utilized to determine the selectivity ratio(SR) for each acid. This may be done with the assistance of gas-liquidchromatography. For example, polyol esters may be saponified to yieldfree fatty acids (FFA) by reacting with NaOH/MeOH. The FFAs may then bemethylated into fatty acid methyl esters (FAMEs) using BF₃/MeOH as theacid catalyst and MeOH as the derivatization reagent. The resultingFAMEs may then be separated using a gas-liquid chromatograph and aredetected with a flame ionization detector (GC/FID). An internal standardmay be used to determine the weight percent of the fatty esters. Therate constants may be calculated by either the use of a computer orgraph.

In addition to the selectivity ratios, the following individual reactionrate constants may be described within the hydrogenation reaction: k₃(C18:3 to C18:2), k₂ (C18:2 to C18:1), and k₁ (C18:1 to C18:0). In someaspects, hydrogenation under conditions sufficient to provide aselectivity or preference for k₂ and/or k₃ (i.e., k₂ and/or k₃ aregreater than k₁) may be used. In these aspects, hydrogenation may beconducted to reduce levels of polyunsaturated compounds within thestarting material or reactants, while minimizing the generation ofsaturated compounds.

In one illustrative embodiment, selective hydrogenation can promotehydrogenation of polyunsaturated fatty acid groups towardmonounsaturated fatty acid groups (having one carbon-carbon doublebond), for example, tri- or diunsaturated fatty acid groups tomonounsaturated groups. In some embodiments, the invention involvesselective hydrogenation of a polyunsaturated polyol ester (such assoybean oil) to a hydrogenation product having a minimum of about 65%monounsaturated fatty acid groups, or a minimum of about 75%monounsaturated fatty acid groups, or a minimum of about 85%monounsaturated fatty acid groups. The target minimum percentage ofmonounsaturated fatty acid groups may depend upon the startingcomposition (i.e., the polyunsaturated polyol ester), since each polyolester may have different starting levels of saturates, monounsaturatesand polyunsaturates. It is also understood that high oleic oils may haveabout 80% or more oleic acid. In such cases, very little hydrogenationmay be required to reduce polyunsaturates.

In one illustrative embodiment, selective hydrogenation can promotehydrogenation of polyunsaturated fatty acid groups in soybean oil towardC18:1, for example, C18:2 to C18:1, and/or C18:3 to C18:2. Selectivehydrogenation of a polyunsaturated composition (e.g., a polyol estersuch as soybean oil) to a hydrogenation product may have reducedpolyunsaturated fatty acid group content, while minimizing completehydrogenation to saturated fatty acid groups (C18:0).

Selective hydrogenation may be accomplished by controlling reactionconditions (such as temperature, rate of heating and/or cooling,hydrogen availability, and catalyst concentration), and/or by selectionof catalyst. For some hydrogenation catalysts, increased temperature orcatalyst concentration may result in an increased selectivity forhydrogenating C18:2 over C18:1. In some aspects, when a nickel-supportedcatalyst is utilized, pressure and/or temperature may be modified toprovide selectivity. Illustrative lower pressures may include pressuresof 50 psi (344.7 kilopascals) or less. Lower pressures can be combined,in some embodiments, with increased temperature to promote selectivity.Illustrative conditions in accordance with these embodiments includetemperatures in the range of 180° C. to 220° C., pressure of about 5 psi(34.47 kilopascals), with nickel catalyst present in an amount of about0.5 wt %. See, for example, Allen et al. “Isomerization DuringHydrogenation. Ill. Linoleic Acid,” JAOC August 1956.

In some aspects, selectivity may be enhanced by diminishing theavailability of hydrogen. For example, reduced reaction pressure and/oragitation rate can diminish hydrogen supply for the reaction.

Selective hydrogenation may be accomplished by selection of thecatalyst. One illustrative catalyst that can enhance selectivity ispalladium. Palladium reaction conditions for sunflower seed oil mayinclude low temperatures (e.g., 40° C.) in ethanol solvent, withcatalyst present in an amount of about 1 wt %. Palladium may be providedon a variety of different supports known for hydrogenation processes.See, for example, Bendaoud Nohaira et al., Palladium supported catalystsfor the selective hydrogenation of sunflower oil,” J. of MolecularCatalysts A: Chemical 229 (2005) 117-126, Nov. 20, 2004.

Optionally, additives such as lead or copper may be included to increaseselectivity. When catalysts containing palladium, nickel or cobalt areused, additives such as amines can be used.

Useful selective hydrogenation conditions are described, for example, inU.S. Pat. Nos. 5,962,711 and 6,265,596. Hydrogenation may be performedby mixing the substrate (polyunsaturated polyol ester), hydrogen gas andsolvent, and bringing the whole mixture into a super-critical ornear-critical state. This substantially homogeneous super-critical ornear-critical solution is led over the catalyst, whereby the reactionproducts formed (i.e., the hydrogenated substrates) will also be a partof the substantially homogeneous super-critical or near-criticalsolution.

Reaction conditions for supercritical hydrogenation may occur over awide experimental range, and this range can be described as follows:temperature (in the range of about 0° C. to about 250° C., or about 20°C. to about 200° C.); pressure (in the range of about 1000 to about35,000 kilopascals, or about 2000 to about 20,000 kilopascals); reactiontime (up to about 10 minutes, or in the range of about 1 second to about1 minute); and solvent concentration (in the range of about 30 wt % toabout 99.9 wt %, or about 40 wt % to about 99 wt %). Useful solventsinclude, for example, ethane, propane, butane, CO₂, dimethyl ether,“freons,” N₂O, N₂, NH₃, or mixtures of these. The catalyst may beselected according to the reaction to be carried out; any usefulcatalyst for hydrogenation can be selected. Concentration of hydrogengas (H₂) can be up to 3 wt %, or in the range of about 0.001 wt % toabout 1 wt %. Concentration of substrate (polyunsaturated polyol ester)in the reaction mixture can be in the range of about 0.1 wt % to about70 wt %, or about 1 wt % to about 60 wt %. A continuous reactor can beused to conduct the hydrogenation reaction, such as described in U.S.Pat. Nos. 5,962,711 and 6,265,596.

The content of the starting material may influence the selectivity.Various substances that are naturally occurring in fats and oils mayinfluence the selectivity of hydrogenation. For example, sulfur is knownto be an irreversible surface poison for nickel catalysts. Othercompounds that may inhibit catalyst activity include phosphatides,nitrogen and halogen derivatives. As a result, a refining step to removesubstances that may have a net negative impact on the hydrogenationprocess may be used. This, in turn, may increase selectivity.

Products of the partial hydrogenation reaction may include one or moreidentifiable properties and/or compounds. Products formed frompolyunsaturated compositions may include characteristic monounsaturatedfatty acid groups in an acid profile and may contain minor amounts ofpolyunsaturated fatty acid groups. In some aspects, the acid profilecomprises polyunsaturated fatty acid groups in an amount of about 1 wt %or less. In some aspects, the starting material may be soybean oil, andthe acid profile of the hydrogenation product may comprise a majority ofmonounsaturated fatty acid groups having a carbon-carbon double bond inthe C₄ to C₁₆ position on the fatty acid or ester. More generallyspeaking, the carbon-carbon double bond may be located on the fatty acidor ester in the C₂ to C(n−1) position, where n is the chain length ofthe fatty acid or ester. The carbon-carbon double bond may be located onthe fatty acid or ester in the C₄ to C(n−2), where n is the chain lengthof the fatty acid or ester. Typically, n may range from about 4 to about30, or from about 4 to about 22.

When the starting material is derived from soybean oil, the acid profileof the partial hydrogenation product composition may comprise saturatedfatty acid groups in an amount that is slightly higher than the startingconcentration of saturated fatty acid groups in the starting material(i.e., unhydrogenated polyunsaturated polyol ester). The acid profile ofthe partial hydrogenation product composition may comprise saturatedfatty acid groups in an amount of about 0.5 wt % to about 10 wt % higherthan the concentration of saturated fatty acid groups in the startingmaterial (polyunsaturated polyol ester starting material). The acidprofile of the partial hydrogenation product composition may comprisesaturated fatty acid groups in an amount of about 0.5 wt % to about 6 wt% higher than the concentration of saturated fatty acid groups in thestarting material. It is understood that partial hydrogenation mayresult in generation of some additional saturated fatty acid groups. Thegeneration of such additional saturated fatty acid groups may becontrolled through selectivity.

As one example of a partial hydrogenation product composition, when thestarting material comprises soybean oil, a partial hydrogenation productcomposition may include saturated fatty acid groups in an amount ofabout 30 wt % or less, or about 25 wt % or less, or about 20 wt % orless. The acid profile may comprise saturated fatty acid groups in anamount in the range of about 15 wt % to about 20 wt %. For soybean oil,illustrative saturated fatty acid groups may include stearic andpalmitic acids. The relative amount and identity of the saturated fattyacids within the partial hydrogenated product composition may vary,depending upon such factors as the starting material (polyunsaturatedpolyol ester), reaction conditions (including catalyst, temperature,pressure, and other factors impacting selectivity of hydrogenation), andpositional isomerization. A representative example of a hydrogenationproduct from selective hydrogenation of soybean oil (SBO) is shown inthe table below.

Percentages of Octadecenoates from Partially Hydrogenated Soybean OilRelative Percent Proposed C18:1 Compounds 0.09 C18:1,4t 0.23 C18:1,5t6.01 C18:1,6-8t 5.88 C18:1,9t 9.75 C18:1,10t 8.64 C18:1,11t 4.89C18:1,12t 6.62 C18:1,13t + 14t (C18:1,6-8c) 14.00 C18:1,9c (Oleic)(C18:1,14-16t) 3.64 C18:1,10c (C18:1,15t) 3.00 C18:1,11c 4.47 C18:1,12c1.02 C18:1,13c 1.16 C18:1,14c (C18:1,16t) Within the above table,isomers are indicated as trans (“t”) or cis (“c”), with the position ofthe double bond immediately preceding the isomer designation. Thus, “4t”is a trans isomer with the double bond at the C4 position within thecarbon chain. Species in parenthesis denote minor products that may bepresent with similar elution times.

The acid profile of the partial hydrogenation product composition fromsoybean oil may comprise at least about 65 wt % monounsaturated fattyacid groups. The acid profile of the partial hydrogenation productcomposition may comprise at least about 70 wt %, or at least about 75 wt%, or at least about 80 wt %, or at least about 85 wt % monounsaturatedfatty acid groups. The monounsaturated fatty acid groups may include thecarbon-carbon double bond at any position from C₂ to C₁₆. Using soybeanoil as an example, the monounsaturated fatty acid groups of the fattyacid profile may include the following:

octadec-2-enoic acid (—OOCCH═CH(CH₂)₁₄CH₃),

octadec-3-enoic acid (—OOC(CH₂)CH═CH(CH₂)₁₃CH₃),

octadec-4-enoic acid (—OOC(CH₂)₂CH═CH(CH₂)₁₂CH₃),

octadec-5-enoic acid (—OOC(CH₂)₃CH═CH(CH₂)₁₁CH₃),

octadec-6-enoic acid (—OOC(CH₂)₄CH═CH(CH₂)₁₀CH₃),

octadec-7-enoic acid (—OOC(CH₂)₅CH═CH(CH₂)₉CH₃),

octadec-8-enoic acid (—OOC(CH₂)₆CH═CH(CH₂)₈CH₃),

octadec-9-enoic acid (—OOC(CH₂)₇CH═CH(CH₂)₇CH₃),

octadec-10-enoic acid (—OOC(CH₂)₈CH═CH(CH₂)₆CH₃),

octadec-11-enoic acid (—OOC(CH₂)₉CH═CH(CH₂)₅CH₃),

octadec-12-enoic acid (—OOC(CH₂)₁₀CH═CH(CH₂)₄CH₃),

octadec-13-enoic acid (—OOC(CH₂)₁₁CH═CH(CH₂)₃CH₃),

octadec-14-enoic acid (—OOC(CH₂)₁₂CH═CH(CH₂)₂CH₃),

octadec-15-enoic acid (—OOC(CH₂)₁₃CH═CH(CH₂)₁CH₃),

octadec-16-enoic acid (—OOC(CH₂)₁₄CH═CHCH₃), and

For each monounsaturated fatty acid, the fatty acid can be the cis ortrans isomer.

An objective of selective hydrogenation may be the reduction in theamount of polyunsaturated fatty acid groups of the polyunsaturatedcomposition (e.g., polyunsaturated polyol ester). The hydrogenationproduct composition may have a polyunsaturated fatty acid group contentof about 10 wt % or less, based upon total fatty acid content in thecomposition. Particularly with respect to the hydrogenation product thatis to be subjected to self-metathesis, hydrogenation may be performed todrive down the concentration of polyunsaturated fatty acid groups evenlower than about 5 wt %, for example to concentrations of about 1 wt %or less, or about 0.75 wt % or less, or about 0.5 wt % or less.

The hydrogenation product composition thus may comprise a reducedpolyunsaturate content relative to the polyunsaturated startingmaterial. The hydrogenation product composition may comprisepolyunsaturated fatty acid groups in an amount of about 1 wt % or less;saturated fatty acid groups in an amount in the range of about 30 wt %or less, or about 25 wt % or less, or about 20 wt % or less; andmonounsaturated fatty acid groups comprising the balance of the mixture,for example, about 65 wt % or more, or about 70 wt % or more, or about75 wt % or more, or about 80 wt % or more, or about 85 wt % or more.This product composition is understood to be illustrative for soybeanoil, and it is understood that the relative amounts of each level ofsaturated, monounsaturated and polyunsaturated components may varydepending upon such factors as the starting material (e.g.,polyunsaturated polyol ester), the hydrogenation catalyst selected, thehydrogenation reaction conditions, and the like factors describedherein.

It may be desirable to maximize the concentration of monounsaturatedfatty acid groups in the hydrogenation product composition. In manyembodiments, the monounsaturated fatty acid groups may comprisemonounsaturated fatty acid groups having the carbon-carbon double bondin the C₄ to C₁₆ position within the carbon chain.

The hydrogenation product composition thus may comprise a partiallyhydrogenated polyol ester. As mentioned previously, in addition toeffecting a reduction of unsaturation of the polyol ester, partialhydrogenation can also cause geometric and positional isomers to beformed. A goal of selective hydrogenation may be reduction in the amountof polyunsaturation in the polyol esters.

The hydrogenation product composition may also be characterized ashaving an iodine number within a desired range. The iodine number is ameasure of the degree of unsaturation of a compound. When used inreference to an unsaturated material, such as an unsaturated polyolester, the iodine number is a measure of the unsaturation, or the numberof carbon-carbon double bonds, of that compound or mixture.

Generally speaking, the iodine number may range from about 8 to about180 in naturally-occurring seed oils, and from about 90 to about 210 innaturally-occurring marine oils. Illustrative iodine numbers for somenatural oils are the following:

Oil Iodine Number soy 125-138 canola 110-115 palm 45-56 rapeseed  97-110sunflower seed 122-139 fish 115-210

At complete hydrogenation of oils or fats, all double bonds would behydrogenated and the iodine number would therefore be zero or near zero.For partially hydrogenated triglycerides the iodine number may be about90 or lower, or about 85 or lower, or about 80 or lower, or about 75 orlower. The iodine number target may depend upon such factors as theinitial iodine number, the content of the monounsaturates in thestarting material, the selectivity of the hydrogenation catalyst, theeconomic optimum level of unsaturation, and the like. An optimum partialhydrogenation would leave only the saturates that were initially presentin the polyunsaturated polyol ester starting material and react all ofthe polyunsaturates. For example, a triolein oil would have an iodinenumber of about 86. Soybean oil starts with an iodine number of around130 with a saturates content of about 15%. An optimum partialhydrogenation product may have an iodine number of about 73 and wouldmaintain the 15% level of saturates. Canola oil has an initial iodinenumber of about 113 and 7% saturates; an optimum partial hydrogenationproduct may have an iodine number of about 80, while maintaining the 7%saturate level. The balance between additional saturate production andallowable polyunsaturate content may depend upon such factors as productquality parameters, yield costs, catalyst costs, and the like. Ifcatalyst costs dominate, then some saturate production may be tolerable.If yield is critical, then some remaining polyunsaturates may betolerable. If the formation of cyclic byproducts is unacceptable, thenit may be acceptable to drive polyunsaturate levels to near zero.

The iodine number may represent a hydrogenation product compositionwherein a certain percentage of double bonds have reacted, on a molarbasis, based upon the starting iodine number of the polyunsaturatedcomposition. For example, soybean oil with an iodine number of about 130may be used as the starting material for the metathesis reactionprocess.

After partial hydrogenation, the hydrogenation catalyst may be removedfrom the partial hydrogenated product using known techniques, forexample, by filtration. The hydrogenation catalyst may be removed usinga plate and frame filter such as those commercially available fromSparkle Filters, Inc., Conroe, Tex. The filtration may be performed withthe assistance of pressure or a vacuum. In order to improve filteringperformance, a filter aid can optionally be used. A filter aid can beadded to the hydrogenated product directly or it can be applied to thefilter. Representative examples of filtering aids include diatomaceousearth, silica, alumina and carbon. Typically, the filtering aid is usedin an amount of about 10 wt % or less, for example, about 5 wt % orless, or about 1 wt % or less. Other filtering techniques and filteringaids can also be employed to remove the used hydrogenation catalyst. Inother embodiments, the hydrogenation catalyst is removed by usingcentrifugation followed by decantation of the product.

Partial hydrogenation of a polyunsaturated composition may impart one ormore desirable properties to the partially hydrogenated composition and,consequently, to chemical (e.g., metathesis) processes performed on thepartially hydrogenated composition. For example, partial hydrogenationmay be used to decrease the amount of polyunsaturated fatty acid groupsin the composition, thereby reducing unneeded sites of reaction for acatalyst. This, in turn, may reduce catalyst demand. Another benefit maybe seen in the final product composition. Because less polyunsaturatedfatty acid groups are present in the reaction mixture prior to thereaction, a more predictable product composition may be provided. Forexample, the carbon chain length and double bond position of productsmay be predicted, based upon the fatty acid composition and catalystutilized. This, in turn, may reduce the purification requirements forthe product composition.

The Metathesis Catalyst

The metathesis reaction may be conducted in the presence of acatalytically effective amount of a metathesis catalyst. The term“metathesis catalyst” includes any catalyst or catalyst system whichcatalyzes the metathesis reaction.

The metathesis catalyst may be used, alone or in combination with one ormore additional catalysts. Exemplary metathesis catalysts may includemetal carbene catalysts based upon transition metals, for example,ruthenium, molybdenum, osmium, chromium, rhenium, and/or tungsten. Themetathesis catalyst may be a metal complex having the structure of thefollowing formula (I)

in which the various substituents are as follows:

-   -   M is ruthenium, molybdenum, osmium, chromium, rhenium, and/or        tungsten.    -   L¹, L² and L³ are neutral electron donor ligands;    -   n is 0 or 1, such that L³ may or may not be present;    -   m is 0, 1, or 2;    -   X¹ and X² are anionic ligands; and

R¹ and R² are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups,

wherein any two or more of X¹, X², L¹, L², L³, R¹, and R² can be takentogether to form a cyclic group, and further wherein any one or more ofX¹, X², L¹, L², L³, R¹, and R² may be attached to a support.

The catalysts may contain Ru, W and/or Mo, with Ru being especiallyadvantageous.

Numerous embodiments of the catalysts useful in the reactions of thedisclosure are described in more detail infra. For the sake ofconvenience, the catalysts are described in groups, but it should beemphasized that these groups are not meant to be limiting in any way.That is, any of the catalysts useful in the disclosure may fit thedescription of more than one of the groups described herein.

A first group of catalysts, which may be referred to as 1^(st)Generation Grubbs-type catalysts, have the structure of formula (I). Forthe first group of catalysts, M and m are as described above, and n, X¹,X², L¹, L², L³, R¹, and R² are described as follows.

For the first group of catalysts, n may be 0, and L¹ and L² mayindependently be phosphine, sulfonated phosphine, phosphite,phosphinite, phosphonite, arsine, stibine, ether, amine, amide, imine,sulfoxide, carboxyl, nitrosyl, pyridine, substituted pyridine,imidazole, substituted imidazole, pyrazine, and/or thioether. Exemplaryligands include trisubstituted phosphines.

X¹ and X² may be anionic ligands, and may be the same or different, ormay be linked together to form a cyclic group which may be a five- toeight-membered ring. X¹ and X² may each be independently hydrogen,halide, or one of the following groups: C₁-C₂₀ alkyl, C₅-C₂₄ aryl,C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₆-C₂₄aryloxycarbonyl, C₂-C₂₄ acyl, C₂-C₂₄ acyloxy, C₁-C₂₀ alkylsulfonato,C₅-C₂₄ arylsulfonato, C₁-C₂₀ alkylsulfanyl, C₅-C₂₄ arylsulfanyl, C₁-C₂₀alkylsulfinyl, or C₅-C₂₄ arylsulfinyl. X¹ and X² may be substituted withone or more moieties selected from C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₂₄aryl, and halide, which may, in turn, with the exception of halide, befurther substituted with one or more groups selected from halide, C₁-C₆alkyl, C₁-C₆ alkoxy, and phenyl. X¹ and X² may be halide, benzoate,C₂-C₆ acyl, C₂-C₆ alkoxycarbonyl, C₁-C₆ alkyl, phenoxy, C₁-C₆ alkoxy,C₁-C₆ alkylsulfanyl, aryl, or C₁-C₆ alkylsulfonyl. X¹ and X² may each behalide, CF₃CO₂, CH₃CO₂, CFH₂CO₂, (CH₃)₃CO, (CF₃)₂(CH₃)CO, (CF₃)(CH₃)₂CO,PhO, MeO, EtO, tosylate, mesylate, or trifluoromethane-sulfonate. X¹ andX² may each be chloride.

R¹ and R² may independently be selected from hydrogen, hydrocarbyl(e.g., C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄alkaryl, C₆-C₂₄ aralkyl, etc.), substituted hydrocarbyl (e.g.,substituted C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl,C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), heteroatom-containing hydrocarbyl(e.g., heteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), andsubstituted heteroatom-containing hydrocarbyl (e.g., substitutedheteroatom-containing C₁-C₂₀ alkyl, C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl,C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, C₆-C₂₄ aralkyl, etc.), and functionalgroups. R¹ and R² may also be linked to form a cyclic group, which maybe aliphatic or aromatic, and may contain substituents and/orheteroatoms. Generally, such a cyclic group may contain 4 to about 12,or 5, 6, 7, or 8 ring atoms.

R¹ may be hydrogen and R² may be selected from C₁-C₂₀ alkyl, C₂-C₂₀alkenyl, C₅-C₂₄ aryl, C₁-C₆ alkyl, C₂-C₆ alkenyl, or C₅-C₁₄ aryl. R² maybe phenyl, vinyl, methyl, isopropyl, or t-butyl, optionally substitutedwith one or more moieties selected from C₁-C₆ alkyl, C₁-C₆ alkoxy,phenyl, or a functional group. R² may be phenyl or vinyl substitutedwith one or more moieties selected from methyl, ethyl, chloro, bromo,iodo, fluoro, nitro, dimethylamino, methyl, methoxy, and phenyl. R² maybe phenyl or —C═C(CH₃)₂.

Any two or more (typically two, three, or four) of X¹, X², L¹, L², L³,R¹, and R² can be taken together to form a cyclic group, as disclosed,for example, in U.S. Pat. No. 5,312,940. When any of X¹, X², L¹, L², L³,R¹, and R² are linked to form cyclic groups, those cyclic groups maycontain 4 to about 12, or 4, 5, 6, 7 or 8 atoms, or may comprise two orthree of such rings, which may be either fused or linked. The cyclicgroups may be aliphatic or aromatic, and may be heteroatom-containingand/or substituted. The cyclic group may form a bidentate ligand or atridentate ligand. Examples of bidentate ligands may includebisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates.

A second group of catalysts, which may be referred to as 2^(nd)Generation Grubbs-type catalysts, have the structure of formula (I),wherein L¹ is a carbene ligand having the structure of formula (II)

such that the complex may have the structure of formula (III)

wherein M, m, n, X¹, X², L², L³, R¹, and R² are as defined for the firstgroup of catalysts, and the remaining substituents are as follows.

X and Y may be heteroatoms typically selected from N, O, S, and P. SinceO and S are divalent, p is zero when X is O or S, and q is zero when Yis O or S. When X is N or P, then p is 1, and when Y is N or P, then qis 1. Both X and Y may be N.

Q¹, Q², Q³, and Q⁴ may be linkers, e.g., hydrocarbylene (includingsubstituted hydrocarbylene, heteroatom-containing hydrocarbylene, andsubstituted heteroatom-containing hydrocarbylene, such as substitutedand/or heteroatom-containing alkylene) or —(CO)—, and w, x, y, and z areindependently zero or 1, meaning that each linker is optional. w, x, y,and z may all be zero. Two or more substituents on adjacent atoms withinQ¹, Q², Q³, and Q⁴ may be linked to form an additional cyclic group.

R³, R^(3A), R⁴, and R^(4A) may be selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, andsubstituted heteroatom-containing hydrocarbyl.

In addition, any two or more of X¹, X², L¹, L², L³, R¹, R², R³, R^(3A),R⁴, and R^(4A) can be taken together to form a cyclic group, and any oneor more of X¹, X², L¹, L², L³, R¹, R², R³, R^(3A), R⁴, and R^(4A) may beattached to a support.

R^(3A) and R^(4A) may be linked to form a cyclic group so that thecarbene ligand is an heterocyclic carbine, for example, anN-heterocyclic carbene, such as the N-heterocyclic carbene having thestructure of formula (IV):

where R³ and R⁴ are defined above at least one of R³ and R⁴, andadvantageously both R³ and R⁴, may be alicyclic or aromatic of one toabout five rings, and optionally containing one or more heteroatomsand/or substituents. Q may be a linker, typically a hydrocarbylenelinker, including substituted hydrocarbylene, heteroatom-containinghydrocarbylene, and substituted heteroatom-containing hydrocarbylenelinkers, wherein two or more substituents on adjacent atoms within Q mayalso be linked to form an additional cyclic structure, which may besimilarly substituted to provide a fused polycyclic structure of two toabout five cyclic groups. Q may comprise a two-atom linkage or athree-atom linkage.

Examples of N-heterocyclic carbene ligands suitable as L¹ may includethe following:

When M is ruthenium, the complex may have the structure of formula (V).

Q may be a two-atom linkage having the structure —CR¹¹R¹²—CR¹³R¹⁴— or—CR¹¹═CR¹³—, wherein R¹¹, R¹², R¹³, and R¹⁴ are independently selectedfrom hydrogen, hydrocarbyl, substituted hydrocarbyl,heteroatom-containing hydrocarbyl, substituted heteroatom-containinghydrocarbyl, and functional groups. Examples of functional groups mayinclude carboxyl, C₁-C₂₀ alkoxy, C₅-C₂₄ aryloxy, C₂-C₂₀ alkoxycarbonyl,C₅-C₂₄ alkoxycarbonyl, C₂-C₂₄ acyloxy, C₁-C₂₀ alkylthio, C₅-C₂₄arylthio, C₁-C₂₀ alkylsulfonyl, and C₁-C₂₀ alkylsulfinyl, optionallysubstituted with one or more moieties selected from C₁-C₁₂ alkyl, C₁-C₁₂alkoxy, C₅-C₁₄ aryl, hydroxyl, sulfhydryl, formyl, and halide. R¹¹, R¹²,R¹³, and R¹⁴ may be independently selected from hydrogen, C1-C12 alkyl,substituted C₁-C₁₂ alkyl, C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂heteroalkyl, phenyl, and substituted phenyl. Any two of R¹¹, R¹², R¹³,and R¹⁴ may be linked together to form a substituted or unsubstituted,saturated or unsaturated ring structure, e.g., a C₄-C₁₂ alicyclic groupor a C₅ or C₆ aryl group, which may itself be substituted, e.g., withlinked or fused alicyclic or aromatic groups, or with othersubstituents.

When R³ and R⁴ are aromatic, they may be composed of one or two aromaticrings, which may or may not be substituted, e.g., R³ and R⁴ may bephenyl, substituted phenyl, biphenyl, substituted biphenyl, or the like.R³ and R⁴ may be the same and each may be unsubstituted phenyl or phenylsubstituted with up to three substituents selected from C₁-C₂₀ alkyl,substituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl, substituted C₁-C₂₀heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, C₅-C₂₄ heteroaryl,C₆-C₂₄ aralkyl, C₆-C₂₄ alkaryl, or halide. Any substituents present maybe hydrogen, C₁-C₁₂ alkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryl, substitutedC₅-C₁₄ aryl, or halide. As an example, R³ and R⁴ may be mesityl.

In a third group of catalysts having the structure of formula (I), M, m,n, X¹, X², R¹, and R² are as defined for the first group of catalysts,L¹ may be a strongly coordinating neutral electron donor ligand such asany of those described for the first and second groups of catalysts, andL² and L³ may be weakly coordinating neutral electron donor ligands inthe form of optionally substituted heterocyclic groups. n is zero or 1,such that L³ may or may not be present. In the third group of catalysts,L² and L³ may be optionally substituted five- or six-membered monocyclicgroups containing 1 to about 4, or 1 to about 3, or 1 to 2 heteroatoms,or are optionally substituted bicyclic or polycyclic structures composedof 2 to about 5 such five- or six-membered monocyclic groups. If theheterocyclic group is substituted, it should not be substituted on acoordinating heteroatom, and any one cyclic moiety within a heterocyclicgroup may not be substituted with more than 3 substituents.

For the third group of catalysts, examples of L² and L³ may include,heterocycles containing nitrogen, sulfur, oxygen, or a mixture thereof.

Examples of nitrogen-containing heterocycles appropriate for L² and L³may include pyridine, bipyridine, pyridazine, pyrimidine, bipyridamine,pyrazine, 1,3,5-triazine, 1,2,4-triazine, 1,2,3-triazine, pyrrole,2H-pyrrole, 3H-pyrrole, pyrazole, 2H-imidazole, 1,2,3-triazole,1,2,4-triazole, indole, 3H-indole, 1H-isoindole, cyclopenta(b)pyridine,indazole, quinoline, bisquinoline, isoquinoline, bisisoquinoline,cinnoline, quinazoline, naphthyridine, piperidine, piperazine,pyrrolidine, pyrazolidine, quinuclidine, imidazolidine, picolylimine,purine, benzimidazole, bisimidazole, phenazine, acridine, and carbazole.

Examples of sulfur-containing heterocycles appropriate for L² and L³ mayinclude thiophene, 1,2-dithiole, 1,3-dithiole, thiepin,benzo(b)thiophene, benzo(c)thiophene, thionaphthene, dibenzothiophene,2H-thiopyran, 4H-thiopyran, and thioanthrene.

Examples of oxygen-containing heterocycles appropriate for L² and L³ mayinclude 2H-pyran, 4H-pyran, 2-pyrone, 4-pyrone, 1,2-dioxin, 1,3-dioxin,oxepin, furan, 2H-1-benzopyran, coumarin, coumarone, chromene,chroman-4-one, isochromen-1-one, isochromen-3-one, xanthene,tetrahydrofuran, 1,4-dioxan, and dibenzofuran.

Examples of mixed heterocycles appropriate for L² and L³ may includeisoxazole, oxazole, thiazole, isothiazole, 1,2,3-oxadiazole,1,2,4-oxadiazole, 1,3,4-oxadiazole, 1,2,3,4-oxatriazole,1,2,3,5-oxatriazole, 3H-1,2,3-dioxazole, 3H-1,2-oxathiole,1,3-oxathiole, 4H-1,2-oxazine, 2H-1,3-oxazine, 1,4-oxazine,1,2,5-oxathiazine, o-isooxazine, phenoxazine, phenothiazine,pyrano[3,4-b]pyrrole, indoxazine, benzoxazole, anthranil, andmorpholine.

The L² and L³ ligands may be aromatic nitrogen-containing andoxygen-containing heterocycles. The L² and L³ ligands may be monocyclicN-heteroaryl ligands that may be optionally substituted with 1 to 3, or1 or 2, substituents. Specific examples of L² and L³ ligands may includepyridine and substituted pyridines, such as 3-bromopyridine,4-bromopyridine, 3,5-dibromopyridine, 2,4,6-tribromopyridine,2,6-dibromopyridine, 3-chloropyridine, 4-chloropyridine,3,5-dichloropyridine, 2,4,6-trichloropyridine, 2,6-dichloropyridine,4-iodopyridine, 3,5-diiodopyridine, 3,5-dibromo-4-methylpyridine,3,5-dichloro-4-methylpyridine, 3,5-dimethyl-4-bromopyridine,3,5-dimethylpyridine, 4-methylpyridine, 3,5-diisopropylpyridine,2,4,6-trimethylpyridine, 2,4,6-triisopropylpyridine,4-(tert-butyl)pyridine, 4-phenylpyridine, 3,5-diphenylpyridine,3,5-dichloro-4-phenylpyridine, and the like.

Any substituents present on L² and/or L³ may be selected from halo,C₁-C₂₀ alkyl, substituted C₁-C₂₀ alkyl, C₁-C₂₀ heteroalkyl, substitutedC₁-C₂₀ heteroalkyl, C₅-C₂₄ aryl, substituted C₅-C₂₄ aryl, C₅-C₂₄heteroaryl, substituted C₅-C₂₄ heteroaryl, C₆-C₂₄ alkaryl, substituted.C₆-C₂₄ alkaryl, C₆-C₂₄ heteroalkaryl, substituted C₆-C₂₄ heteroalkaryl,C₆-C₂₄ aralkyl, substituted C₆-C₂₄ aralkyl, C₆-C₂₄ heteroaralkyl,substituted C₆-C₂₄ heteroaralkyl, and functional groups, with suitablefunctional groups including, without limitation, C₁-C₂₀ alkoxy, C₅-C₂₄aryloxy, C₂-C₂₀ alkylcarbonyl, C₆-C₂₄ arylcarbonyl, C₂-C₂₀alkylcarbonyloxy, C₆-C₂₄ arylcarbonyloxy, C₂-C₂₀ alkoxycarbonyl, C₆-C₂₄aryloxycarbonyl, halocarbonyl, C₂-C₂₀ alkylcarbonato, C₆-C₂₄arylcarbonato, carboxy, carboxylato, carbamoyl, mono-(C₁-C₂₀alkyl)-substituted carbamoyl, di-(C₁-C₂₀ alkyl)-substituted carbamoyl,di-N—(C₁-C₂₀ alkyl), N—(C₅-C₂₄ aryl)-substituted carbamoyl, mono-(C₅-C₂₄aryl)-substituted carbamoyl, di-(C₆-C₂₄ aryl)-substituted carbamoyl,thiocarbamoyl, mono-(C₁-C₂₀ alkyl)-substituted thiocarbamoyl, di-(C₁-C₂₀alkyl)-substituted thiocarbamoyl, di-N—(C₁-C₂₀ alkyl)-N—(C₆-C₂₄aryl)-substituted thiocarbamoyl, mono-(C₆-C₂₄ aryl)-substitutedthiocarbamoyl, di-(C₆-C₂₄ aryl)-substituted thiocarbamoyl, carbamido,formyl, thioformyl, amino, mono-(C₁-C₂₀ alkyl)-substituted amino,di-(C₁-C₂₀ alkyl)-substituted amino, mono-(C₅-C₂₄ aryl)-substitutedamino, di-(C₅-C₂₄ aryl)-substituted amino, di-N—(C₁-C₂₀ alkyl),N—(C₅-C₂₄ aryl)-substituted amino, C₂-C₂₀ alkylamido, C₆-C₂₄ arylamido,imino, C₁-C₂₀ alkylimino, C₅-C₂₄ arylimino, nitro, and nitroso. Inaddition, two adjacent substituents may be taken together to form aring, generally a five- or six-membered alicyclic or aryl ring,optionally containing 1 to about 3 heteroatoms and 1 to about 3substituents.

The substituents on L² and L³ may include halo, C₁-C₁₂ alkyl,substituted C₁-C₁₂ alkyl, C₁-C₁₂ heteroalkyl, substituted C₁-C₁₂heteroalkyl, C₅-C₁₄ aryl, substituted C₅-C₁₄ aryl, C₅-C₁₄ heteroaryl,substituted C₅-C₁₄ heteroaryl, C₆-C₁₆ alkaryl, substituted C₆-C₁₆alkaryl, C₆-C₁₆ heteroalkaryl, substituted C₆-C₁₆ heteroalkaryl, C₆-C₁₆aralkyl, substituted C₆-C₁₆ aralkyl, C₆-C₁₆ heteroaralkyl, substitutedC₆-C₁₆ heteroaralkyl, C₁-C₁₂ alkoxy, C₅-C₁₄ aryloxy, C₂-C₁₂alkylcarbonyl, C₆-C₁₄ arylcarbonyl, C₂-C₁₂ alkylcarbonyloxy, C₆-C₁₄arylcarbonyloxy, C₂-C₁₂ alkoxycarbonyl, C₆-C₁₄ aryloxycarbonyl,halocarbonyl, formyl, amino, mono-(C₁-C₁₂ alkyl)-substituted amino,di-(C₁-C₁₂ alkyl)-substituted amino, mono-(C₅-C₁₄ aryl)-substitutedamino, di-(C₅-C₁₄ aryl)-substituted amino, and nitro.

The substituents may be halo, C₁-C₆ alkyl, C₁-C₆ haloalkyl, C₁-C₆alkoxy, phenyl, substituted phenyl, formyl, N,N-diC₁-C₆ alkyl)amino,nitro, or nitrogen heterocycles as described above (including, forexample, pyrrolidine, piperidine, piperazine, pyrazine, pyrimidine,pyridine, pyridazine, etc.).

L² and L³ may also be taken together to form a bidentate or multidentateligand containing two or more, generally two, coordinating heteroatomssuch as N, O, S, or P. These may include diimine ligands of theBrookhart type. A representative bidentate ligand has the structure offormula (VI)

wherein R¹⁵, R¹⁶, R¹⁷, and R¹⁸ may be hydrocarbyl (e.g., C₁-C₂₀ alkyl,C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, or C₆-C₂₄aralkyl), substituted hydrocarbyl (e.g., substituted C₁-C₂₀ alkyl,C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₅-C₂₄ aryl, C₆-C₂₄ alkaryl, or C₆-C₂₄aralkyl), heteroatom-containing hydrocarbyl (e.g., C₁-C₂₀ heteroalkyl,C₅-C₂₄ heteroaryl, heteroatom-containing C₆-C₂₄ aralkyl, orheteroatom-containing C₆-C₂₄ alkaryl), or substitutedheteroatom-containing hydrocarbyl (e.g., substituted C₁-C₂₀ heteroalkyl,C₅-C₂₄ heteroaryl, heteroatom-containing C₆-C₂₄ aralkyl, orheteroatom-containing C₆-C₂₄ alkaryl), or (1) R¹⁵ and R¹⁶, (2) R¹⁷ andR¹⁸, (3) R¹⁶ and R¹⁷, or (4) both R¹⁵ and R¹⁶, and R¹⁷ and R¹⁸, may betaken together to form a ring, i.e., an N-heterocycle. Preferred cyclicgroups in such a case are five- and six-membered rings, typicallyaromatic rings.

In a fourth group of catalysts that have the structure of formula (I),two of the substituents may be taken together to form a bidentate ligandor a tridentate ligand. Examples of bidentate ligands may includebisphosphines, dialkoxides, alkyldiketonates, and aryldiketonates. Thesemay include —P(Ph)₂CH₂CH₂P(Ph)₂-, —As(Ph)₂CH₂CH₂As(Ph₂)—,—P(Ph)₂CH₂CH₂C(CF₃)₂O—, binaphtholate dianions, pinacolate dianions,—P(CH₃)₂(CH₂)₂P(CH₃)₂—, and —OC(CH₃)₂(CH₃)₂CO—. Preferred bidentateligands are —P(Ph)₂CH₂CH₂P(Ph)₂- and —P(CH₃)₂(CH₂)₂P(CH₃)₂—. Tridentateligands include, but are not limited to,(CH₃)₂NCH₂CH₂P(Ph)CH₂CH₂N(CH₃)₂. Other tridentate ligands may be thosein which any three of X¹, X², L¹, L², L³, R¹, and R² (e.g., X¹, L¹, andL²) are taken together to be cyclopentadienyl, indenyl, or fluorenyl,each optionally substituted with C₂-C₂₀ alkenyl, C₂-C₂₀ alkynyl, C₁-C₂₀alkyl, C₅-C₂₀ aryl, C₁-C₂₀ alkoxy, C₂-C₂₀ alkenyloxy, C₂-C₂₀ alkynyloxy,C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₁-C₂₀ alkylthio, C₁-C₂₀alkylsulfonyl, or C₁-C₂₀ alkylsulfinyl, each of which may be furthersubstituted with C₁-C₆ alkyl, halide, C₁-C₆ alkoxy or with a phenylgroup optionally substituted with halide, C₁-C₆ alkyl, or C₁-C₆ alkoxy.In compounds of this type, X, L¹, and L² may be taken together to becyclopentadienyl or indenyl, each optionally substituted with vinyl,C₁-C₁₀ alkyl, C₅-C₂₀ aryl, C₁-C₁₀ carboxylate, C₂-C₁₀ alkoxycarbonyl,C₁-C₁₀ alkoxy, or C₅-C₂₀ aryloxy, each optionally substituted with C₁-C₆alkyl, halide, C₁-C₆ alkoxy or with a phenyl group optionallysubstituted with halide, C₁-C₆ alkyl or C₁-C₆ alkoxy. X, L¹ and L² maybe taken together to be cyclopentadienyl, optionally substituted withvinyl, hydrogen, methyl, or phenyl. Tetradentate ligands may includeO₂C(CH₂)₂P(Ph)(CH₂)₂P(Ph)(CH₂)₂CO₂, phthalocyanines, and porphyrins.

Complexes wherein L² and R² are linked are examples of the fourth groupof catalysts. These may be called “Grubbs-Hoveyda” catalysts. Examplesof Grubbs-Hoveyda-type catalysts may include the following:

wherein L¹, X¹, X², and M are as described for any of the other groupsof catalysts.

In addition to the catalysts that have the structure of formula (I), asdescribed above, other transition metal carbene complexes may include;

neutral ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 16, are penta-coordinated, and are of the general formula(VII);

neutral ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 18, are hexa-coordinated, and are of the general formula(VIII);

cationic ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 14, are tetra-coordinated, and are of the general formula (IX);and

cationic ruthenium or osmium metal carbene complexes containing metalcenters that are formally in the +2 oxidation state, have an electroncount of 14, are tetra-coordinated, and are of the general formula (X)

wherein: X¹, X², L¹, L², n, L³, R¹, and R² may be as defined for any ofthe previously defined four groups of catalysts; r and s areindependently zero or 1; t may be an integer in the range of zero to 5;

Y may be any non-coordinating anion (e.g., a halide ion, BF₄ ⁻, etc.);Z¹ and Z² may be independently selected from —O—, —S—, —NR²—, —PR²—,—P(═O)R²—, —P(OR²)—, —P(═O)(OR²)—, —C(═O)—, —C(═O)O—, —OC(═O)—,—OC(═O)O—, —S(═O)—, and —S(═O)₂—; Z³ may be any cationic moiety such as—P(R²)₃ ⁺ or —N(R²)₃ ⁺; and

any two or more of X¹, X², L¹, L², L³, n, Z¹, Z², Z³, R¹, and R² may betaken together to form a cyclic group, e.g., a multidentate ligand, and

wherein any one or more of X¹, X², L¹, L², n, L³, Z¹, Z², Z³, R¹ and R²may be attached to a support.

Other suitable complexes include Group 8 transition metal carbenesbearing a cationic substituent, such as are disclosed in U.S. Pat. No.7,365,140 (Piers et al.) having the general structure (XI):

wherein:

M is a Group 8 transition metal;

L¹ and L² are neutral electron donor ligands;

X¹ and X² are anionic ligands;

R¹ is hydrogen, C₁-C₁₂ hydrocarbyl, or substituted C₁-C₁₂ hydrocarbyl;

W is an optionally substituted and/or heteroatom-containing C₁-C₂₀hydrocarbylene linkage;

Y is a positively charged Group 15 or Group 16 element substituted withhydrogen, C₁-C₁₂ hydrocarbyl, substituted C₁-C₁₂ hydrocarbyl;heteroatom-containing C₁-C₁₂ hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl;

Z⁻ is a negatively charged counterion;

m is zero or 1; and

n is zero or 1;

-   -   wherein any two or more of L¹, L², X¹, X², R¹, W, and Y can be        taken together to form a cyclic group.

Each of M, L¹, L², X¹, and X² in structure (XI) may be as previouslydefined herein.

W may be an optionally substituted and/or heteroatom-containing C₁-C₂₀hydrocarbylene linkage, typically an optionally substituted C₁-C₁₂alkylene linkage, e.g., —(CH₂)_(i)— where i is an integer in the rangeof 1 to 12 inclusive and any of the hydrogen atoms may be replaced witha non-hydrogen substituent as described earlier herein with regard tothe definition of the term “substituted.” The subscript n may be zero or1, meaning that W may or may not be present. In an embodiment, n iszero.

Y may be a positively charged Group 15 or Group 16 element substitutedwith hydrogen, C₁-C₁₂ hydrocarbyl, substituted C₁-C₁₂ hydrocarbyl,heteroatom-containing C₁-C₁₂ hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl. Y may be a C₁-C₁₂hydrocarbyl-substituted, positively charged Group 15 or Group 16element. Representative Y groups may include P(R²)₃, P(R²)₃, As(R²)₃,S(R²)₂, O(R²)₂, where the R² may be independently selected from C₁-C₁₂hydrocarbyl. Within these, the Y groups may be phosphines of thestructure P(R²)₃ wherein the R² may be independently selected fromC₁-C₁₂ alkyl and aryl, and thus include, for example, methyl, ethyl,n-propyl, isopropyl, n-butyl, isobutyl, t-butyl, cyclopentyl,cyclohexyl, and phenyl. Y may also be a heterocyclic group containingthe positively charged Group 15 or Group 16 element. For instance, whenthe Group 15 or Group 16 element is nitrogen, Y may be an optionallysubstituted pyridinyl, pyrazinyl, or imidazolyl group.

Z⁻ may be a negatively charged counterion associated with the cationiccomplex, and may be virtually any anion, so long as the anion is inertwith respect to the components of the complex and the reactants andreagents used in the metathesis reaction. The Z⁻ moieties may be weaklycoordinating anions, such as, for instance, [B(C₆F₅)₄]⁻, [BF₄]⁻,[B(C₆H₆)₄]⁻, [CF₃S(O)₃]⁻, [PF₆]⁻, [SbF₆]⁻, [AlCl₄]⁻, [FSO₃]⁻,[CB₁₁H₆Cl₆]⁻, [CB₁₁H₆Br₆]⁻, and [SO₃F:SbF₅]⁻. Anions suitable as Z⁻ maybe of the formula B(R¹⁵)₄ ⁻ where R¹⁵ is fluoro, aryl, or perfluorinatedaryl, typically fluoro or perfluorinated aryl. Anions suitable as Z⁻ maybe BF₄ ⁻ or B(C₆F₅)⁻.

Any two or more of X¹, X², L¹, L², W, and Y may be taken together toform a cyclic group, as disclosed, for example, in U.S. Pat. No.5,312,940. When any of X¹, X², L¹, L², R¹, W, and Y are linked to formcyclic groups, those cyclic groups may be five- or six-membered rings,or may comprise two or three five- or six-membered rings, which may beeither fused or linked. The cyclic groups may be aliphatic or aromatic,and may be heteroatom-containing and/or substituted.

One group of exemplary catalysts encompassed by the structure of formula(XI) are those wherein m and n are zero, such that the complex has thestructure of formula (XII)

The X¹, X², and L¹ ligands are as described earlier with respect tocomplexes of formula (XI), as are Y⁺ and Z⁻. M may be Ru or Os and R¹may be hydrogen or C₁-C₁₂ alkyl. M may be Ru, and R¹ may be hydrogen.

In formula (XII)-type catalysts, L¹ may be a heteroatom-containingcarbene ligand having the structure of formula (XIII)

such that complex (XII) has the structure of formula (XIV)

wherein X¹, X², R¹, R², Y, and Z are as defined previously, and theremaining substituents are as follows:

Z¹ and Z² may be heteroatoms typically selected from N, O, S, and P.Since O and S are divalent, j may be zero when Z¹ is O or S, and k maybe zero when Z² is O or S. However, when Z¹ is N or P, then j may be 1,and when Z² is N or P, then k may be 1. Both Z¹ and Z² may be N.

Q¹, Q², Q³, and Q⁴ are linkers, e.g., C₁-C₁₂ hydrocarbylene, substitutedC₁-C₁₂ hydrocarbylene, heteroatom-containing C₁-C₁₂ hydrocarbylene,substituted heteroatom-containing C₁-C₁₂ hydrocarbylene, or —(CO)—, andw, x, y, and z may be independently zero or 1, meaning that each linkermay be optional. w, x, y, and z may all be zero.

R³, R^(3A), R⁴, and R^(4A) may be selected from hydrogen, C₁-C₂₀hydrocarbyl, substituted C₁-C₂₀ hydrocarbyl, heteroatom-containingC₁-C₂₀ hydrocarbyl, and substituted heteroatom-containing C₁-C₂₀hydrocarbyl.

w, x, y, and z may be zero, Z¹ and Z¹ may be N, and R^(3A) and R^(4A)may be linked to form -Q-, such that the complex has the structure offormula (XV)

wherein R³ and R⁴ are defined above. At least one of R³ and R⁴, andoptionally both R³ and R⁴, may be alicyclic or aromatic of one to aboutfive rings, and optionally containing one or more heteroatoms and/orsubstituents. Q may be a linker, typically a hydrocarbylene linker,including C₁-C₁₂ hydrocarbylene, substituted C₁-C₁₂ hydrocarbylene,heteroatom-containing C₁-C₁₂ hydrocarbylene, or substitutedheteroatom-containing C₁-C₁₂ hydrocarbylene linker, wherein two or moresubstituents on adjacent atoms within Q may be linked to form anadditional cyclic structure, which may be similarly substituted toprovide a fused polycyclic structure of two to about five cyclic groups.Q may be a two-atom linkage or a three-atom linkage, e.g., —CH₂—CH₂—,—CH(Ph)-CH(Ph)- where Ph is phenyl; ═CR—N═, giving rise to anunsubstituted (when R═H) or substituted (R=other than H) triazolylgroup; or —CH₂—SiR₂—CH₂— (where R is H, alkyl, alkoxy, etc.).

Q may be a two-atom linkage having the structure —CR⁸R⁹—CR¹⁰R¹¹— or—CR⁸═CR¹⁰—, wherein R⁸, R⁹, R¹⁰, and R¹¹ may be independently selectedfrom hydrogen, C₁-C₁₂ hydrocarbyl, substituted C₁-C₁₂ hydrocarbyl,heteroatom-containing C₁-C₁₂ hydrocarbyl, substitutedheteroatom-containing C₁-C₁₂ hydrocarbyl, and functional groups.Examples of the functional groups may include carboxyl, C₁-C₂₀ alkoxy,C₅-C₂₀ aryloxy, C₂-C₂₀ alkoxycarbonyl, C₂-C₂₀ alkoxycarbonyl, C₂-C₂₀acyloxy, C₁-C₂₀ alkylthio, C₅-C₂₀ arylthio, C₁-C₂₀ alkylsulfonyl, andC₁-C₂₀ alkylsulfinyl, optionally substituted with one or more moietiesselected from C₁-C₁₀ alkyl, C₁-C₁₀ alkoxy, C₅-C₂₀ aryl, hydroxyl,sulfhydryl, formyl, and halide. Alternatively, any two of R⁸, R⁹, R¹⁰,and R¹¹ may be linked together to form a substituted or unsubstituted,saturated or unsaturated ring structure, e.g., a C₄-C₁₂ alicyclic groupor a C₅ or C₆ aryl group, which may itself be substituted, e.g., withlinked or fused alicyclic or aromatic groups, or with othersubstituents.

Further details concerning such formula (XI) complexes, as well asassociated preparation methods, may be obtained from U.S. Pat. No.7,365,140.

Suitable solid supports for any of the catalysts described herein may bemade of synthetic, semi-synthetic, or naturally occurring materials,which may be organic or inorganic, e.g., polymeric, ceramic, ormetallic. Attachment to the support may be covalent, and the covalentlinkage may be direct or indirect, if indirect, typically through afunctional group on a support surface.

Examples of the catalysts that may be used may include the following,some of which for convenience are identified throughout this disclosureby reference to their molecular weight:

In the foregoing molecular structures and formulae, Ph representsphenyl, Cy represents cyclohexane, Me represents methyl, nBu representsn-butyl, i-Pr represents isopropyl, py represents pyridine (coordinatedthrough the N atom), and Mes represents mesityl (i.e.,2,4,6-trimethylphenyl).

Further examples of catalysts that may be used may include thefollowing: ruthenium (II)dichloro(3-methyl-1,2-butenylidene)bis(tricyclopentylphosphine) (C716);ruthenium (II)dichloro(3-methyl-1,2-butenylidene)bis(tricyclohexylphosphine) (C801);ruthenium (II) dichloro(phenylmethylene)bis(tricyclohexylphosphine)(C823); ruthenium (II)[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(triphenylphosphine)(C830), and ruthenium (II) dichloro(vinylphenylmethylene)bis(tricyclohexylphosphine) (C835); ruthenium (II)dichloro(tricyclohexylphosphine)(o-isopropoxyphenylmethylene) (C601),and ruthenium (II)(1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(bis3-bromopyridine (C884)).

Exemplary ruthenium-based metathesis catalysts may include thoserepresented by structures 12 (commonly known as Grubbs's catalyst), 14and 16. Structures 18, 20, 22, 24, 26, 28, 60, 62, 64, 66, and 68represent additional ruthenium-based metathesis catalysts. CatalystsC627, C682, C697, C712, and C827 represent still additionalruthenium-based catalysts. General structures 50 and 52 representadditional ruthenium-based metathesis catalysts of the type reported inChemical & Engineering News; Feb. 12, 2007, at pages 37-47. In thestructures, Ph is phenyl, Mes is mesityl, py is pyridine, Cp iscyclopentyl, and Cy is cyclohexyl.

Techniques for using the metathesis catalysts are known in the art (see,for example, U.S. Pat. Nos. 7,102,047; 6,794,534; 6,696,597; 6,414,097;6,306,988; 5,922,863; 5,750,815; and metathesis catalysts with ligandsin U.S. Patent Publication No. 2007/0004917 A1). A number of themetathesis catalysts as shown are manufactured by Materia, Inc.(Pasadena, Calif.).

Additional exemplary metathesis catalysts may include metal carbenecomplexes selected from molybdenum, osmium, chromium, rhenium, andtungsten. The term “complex” refers to a metal atom, such as atransition metal atom, with at least one ligand or complexing agentcoordinated or bound thereto. Such a ligand may be a Lewis base in metalcarbene complexes useful for alkyne or alkene-metathesis. Typicalexamples of such ligands include phosphines, halides and stabilizedcarbenes. Some metathesis catalysts may employ plural metals or metalco-catalysts (e.g., a catalyst comprising a tungsten halide, atetraalkyl tin compound, and an organoaluminum compound).

An immobilized catalyst can be used for the metathesis process. Animmobilized catalyst may be a system comprising a catalyst and asupport, the catalyst associated with the support. Exemplaryassociations between the catalyst and the support may occur by way ofchemical bonds or weak interactions (e.g. hydrogen bonds, donor acceptorinteractions) between the catalyst, or any portions thereof, and thesupport or any portions thereof. Support may be any material suitable tosupport the catalyst. Typically, immobilized catalysts may be solidphase catalysts that act on liquid or gas phase reactants and products.Exemplary supports may include polymers, silica or alumina. Such animmobilized catalyst may be used in a flow process. An immobilizedcatalyst may simplify purification of products and recovery of thecatalyst so that recycling the catalyst may be more convenient.

Polymerizaiton of the Functionalized Monomers

One or more of the functionalized monomers may be polymerized to form afunctionalized polymer (or oligomer) or copolymerized with one or morecomonomers to form a functionalized copolymer (or co-oligomer). The term“polymer” is used herein to refer to polymers and copolymers, as well asoligomers and co-oligomers. The term “polymerize” is used herein toinclude polymerization reactions, co-polymerization reactions,oligomerization reactions and co-oligomerization reactions. Thefunctionalized monomers and functionalized polymers may have utility inmany applications including lubricants, functional fluids, fuels, moldedor extruded articles, pharmaceuticals, cosmetics, personal careproducts, adhesives, coatings, pharmaceuticals, cosmetics, personal careproducts, industrial cleaners, institutional cleaners, foods, beverages,oil field chemicals, agricultural chemicals, and the like. Thefunctionalized monomers and polymers may be used as base oils forlubricants and functional fluids, and/or as functional additives forlubricants, functional fluids and fuels. The functionalized polymers maybe referred to as polymeric resins.

The comonomer may comprise an olefin, acrylic acid, acrylic acid ester,methacrylic acid, methacrylic acid ester, unsaturated nitrile, vinylester, vinyl ether, halogenated monomer, unsaturated polycarboxylic acidor derivative thereof, polyhydric alcohol, polyamine, polyalkylenepolyamine, isocyanate, diisocyanate, alkenyl-substituted aromaticcompound (e.g., styrene), alkenyl-substituted heterocyclic compound,organosilane, or a mixture of two or more thereof.

The olefin comonomer may contain from 2 to about 30 carbon atoms, orfrom 2 to about 24 carbon atoms, or from about 6 to about 24 carbonatoms. The olefin comonomer may comprise an alpha olefin, an internalolefin, or a mixture thereof. The internal olefin may be symmetric orasymmetric. The olefin may be linear or branched. The olefin may be amonoene, diene, triene, tetraene, or mixture of two or more thereof. Themonoenes may comprise one or more of ethene, 1-propene, 1-butene,2-butene, isobutene, 1-pentene, 2-pentene, 3-pentene, cyclopentene,1-hexene, 2-hexene, 3-hexene, cyclohexene, 1-heptene, 2-heptene,3-heptene, 1-octene, 2-octene, 3-octene, 1-nonene, 2-nonene, 3-nonene,4-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene,1-pentadecene, 1-hexadecene, 1-octadecene, 1-eicosene,2-methyl-1-butene, 2-methyl-2-butene, 3-methyl-1-butene,2-methyl-1-pentene, 3-methyl-1-pentene, 4-methyl-1-pentene,2-methyl-2-pentene, 3-methyl-2-pentene, 4-methyl-2-pentene,2-methyl-3-pentene, 2,2-dimethyl-3-pentene, styrene, vinyl cyclohexane,or a mixture of two or more thereof. The dienes, trienes and tetraenesmay comprise butadiene, isoprene, hexadiene, decadiene, octatriene,ocimene, farnesene, or a mixture of two or more thereof.

The alphaolefin may comprise ethene, 1-propene, 1-butene, 1-pentene,1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene,1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-octadecene,1-eicosene, or a mixture of two or more thereof.

The olefin comonomer may be a conjugated diene. The conjugated diene mayinclude one or more dienes containing from 4 to about 12 carbon atoms,or from about 4 to about 8 carbon atoms. Examples may include1,3-butadiene, isoprene, 1,3-pentadiene, 1,3-hexadiene,2-ethylbutadiene, 2-propylbutadiene, 2-propyl butadiene,2-butylbutadiene, 2-octylbutadiene, 4-methylpentadiene,2,3-dimethylbutadiene, 2-phenyl butadiene, 1-chlorobutadiene,2-methoxybutadiene, or a mixture of two or more thereof.

The acrylic acids, acrylic acid esters, methacrylic acids andmethacrylic acid esters (which collectively may be referred to as (meth)acrylic acids and/or esters) may be represented by the followingformula:

CH₂═C(R₁)C(O)OR₂

wherein R₁ is hydrogen or a methyl group, and R₂ is hydrogen or ahydrocarbyl group containing from 1 to about 30 carbon atoms, or from 1to about 20, or from 1 to about 10 carbon atoms, and optionally, one ormore sulfur, nitrogen, phosphorus, silicon, halogen and/or oxygen atoms.Examples may include methyl(meth)acrylate, ethyl(meth)acrylate,propyl(meth)acrylate, butyl(meth)acrylate, amyl(meth)acrylate,hexyl(meth)acrylate, 2-hydroxyethyl(meth)acrylate,2-hydroxypropyl(meth)acrylate, 4-hydroxybutyl(meth)acrylate,N,N-dimethylaminoethyl(meth)acrylate,N,N-diethylaminoethyl(meth)acrylate, 2-sulfoethyl(meth)acrylate,trifluoroethyl(meth)acrylate, glycidyl(meth)acrylate,benzyl(meth)acrylate, 2-chloroethyl(meth)acrylate,2-ethylhexyl(meth)acrylate, phenyl(meth)acrylate, acrylamide, andmixtures of two or more thereof.

The unsaturated nitriles may comprise acrylonitrile or C₁-C₄ alkylderivatives thereof. These may include acrylonitrile, methacrylonitrile,and the like.

The alkenyl-substituted aromatic compounds may comprise an alkenyl groupattached to an aromatic group. The alkenyl group may contain from 2 toabout 30 carbon atoms. The alkenyl group may include a carbon-carbondouble bond in alpha-position to the aromatic group. The alkenyl groupmay be a vinyl group. The aromatic group may be mononuclear, such asphenyl, or polynuclear. The polynuclear compounds or groups may be ofthe fused type wherein an aromatic nucleus is fused at two points toanother nucleus such as found in anthranyl. The polynuclear group may beof the linked type wherein at least two nuclei (either mononuclear orpolynuclear) are linked through bridging linkages to each other. Thebridging linkages may include carbon-to-carbon single bonds, etherlinkages, keto linkages, sulfide linkages, polysulfide linkages of 2 toabout 6 sulfur atoms, sulfinyl linkages, sulfonyl linkages, alkylenelinkages, alkylidene linkages, alkylene ether linkages, alkylene ketolinkages, alkylene sulfur linkages, alkylene polysulfide linkages, aminolinkages, polyamino linkages, mixtures of such divalent bridginglinkages, and the like. Examples may include styrene; ortho, meta, orpara-methylstyrene; ortho-, meta- or para-ethylstyrene;o-methyl-p-isopropylstyrene; p-chlorostyrene; p-bromostyrene; ortho-,meta- or para-methoxystyrene; vinylnaphthalene; and mixtures of two ormore thereof.

The vinyl ester monomers may be derived from carboxylic acids containing1 to about 30, or 1 to about 20, or 1 to about 10 carbon atoms. Thesemay include vinyl acetate, vinyl propionate, vinyl hexanoate, vinyl2-ethylhexanoate, vinyl octanoate, vinyl laurate, and mixtures of two ormore thereof. The vinyl ethers may include methyl-, ethyl-, and/or butylvinyl ethers.

The halogenated monomers, that is, fluorine, chlorine, bromine, and/oriodine-containing monomers, may contain from 2 to about 30 carbon atomsand at least one halogen atom. These may include vinyl halides. Examplesof these monomers may include vinyl fluoride, vinyl chloride, vinylbromide, vinylidene fluoride, vinylidene chloride,halogenated(meth)acrylic acid, allyl chloride and mixtures of two ormore thereof.

The unsaturated polycarboxylic acids and derivatives thereof may includeunsaturated polycarboxylic acids and their corresponding anhydrides.These may include those which have at least one ethylenic linkage in analpha, beta-position with respect to at least one carboxyl group.Exemplary acids and anhydrides may include maleic acid, maleicanhydride, fumaric acid, itaconic acid, itaconic anhydride, citraconicacid, citraconic anhydride, mesaconic acid, mesaconic anhydride,glutaconic acid, glutaconic anhydride, chloromaleic acid, aconitic acid,mixtures of two or more thereof, and the like.

The polyhydric alcohols may contain from 2 to about 10 carbon atoms, andfrom 2 to about 6 hydroxyl groups. Examples may include ethylene glycol,glycerol, trimethylolpropane, 1,2-propanediol, 1,3-propanediol,1,2-butanediol, 1,3-butanediol, 2,3-butanediol, 2-ethyl-1,3-propanediol,2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, pentaerythritol, sorbitol, mixtures oftwo or more thereof, and the like.

The polyamines and polyalkylene polyamines may be represented by theformula

wherein each R is independently hydrogen, a hydrocarbyl group or ahydroxy-substituted hydrocarbyl group containing up to about 30 carbonatoms, or up to about 10 carbon atoms, with the proviso that at leasttwo of the R groups are hydrogen, n is a number in the range from 1 toabout 10, or from about 2 to about 8, and R¹ is an alkyene groupcontaining 1 to about 18 carbon atoms, or 1 to about 10 carbon atoms, orfrom about 2 to about 6 carbon atoms. Examples of these polyamines mayinclude methylene polyamine, ethylene polyamine, propylene polyamine,butylenes polyamine, pentylene polyamine, hexylene polyamine, heptylenepolyamine, ethylene diamine, triethylene tetramine,tris(2-aminoethyl)amine, propylene diamine, trimethylene diamine,hexamethylene diamine, decamethylene diamine, octamethylene diamine,di(heptamethylene)triamine, tripropylene tetramine, tetraethylenepentamine, trimethylene diamine, pentaethylene hexamine,di(trimethylene)triamine, 2-heptyl-3-(2-aminopropyl)imidazoline,1,3-bis(2-amino-ethyl)piperazine, 1,4-bis(2-aminoethyl)piperazine,2-methyl-1-(2-aminobutyl)piperazine, or a mixture of two or morethereof.

The isocyanate monomers may include one or more isocyanate groups(—N═C═O). These may include monoisocyanates and diisocyanates. Examplesmay include methyl isocyanate, methylene diphenyl diisocyanate, toluenediisocyanate, isophorone diisocyanate, and mixtures of two or morethereof.

The alkenyl-substituted heterocyclic monomers may include heterocycliccompounds wherein the hetero atom is N, O or S. The alkenyl group maycontain from 2 to about 30 carbon atoms. The alkenyl group may be avinyl group. The heterocyclic group may be a 5 or 6 member ring.Examples may include vinyl pyridine, N-vinyl pyrolidone, mixturesthereof, and the like.

The organosilanes may include gamma-aminopropyltrialkoxysilanes,gamma-isocyanatopropyltriethoxysilane, vinyl-trialkoxysilanes,glycidoxypropyltrialkoxysilanes, ureidopropyltrialkoxysilanes, andmixtures of two or more thereof.

The olefin comonomer may comprise 1-decene, and the functionalizedmonomer may comprise an ester of 8-nonenoic acid, an ester of 9-decenoicacid, an ester of 10-undecenoic acid, an ester of 9-dodecenoic acid, amono- or di-ester of 9-octadecenedioic acid, or a mixture of two or morethereof. The esters may be methyl esters.

The olefin comonomer may comprise 1-octene, 1-decene, 1-dodecene, or amixture of two or more thereof, and the functionalized monomer maycomprise methyl 9-decenoate.

The olefin comonomer may comprise 1-octene, 1-decene, dodecene, or amixture of two or more thereof, and the functionalized monomer maycomprise a pentaerythritol tetra-ester of 9-decenoic acid.

Transesterification of an ester (e.g., methyl ester) of 8-decenoic acid,9-decenoic acid, 10-undecenoic acid, 9-dodecenoic acid, 9-octadecenoicacid, or a mixture of two or more thereof, with pentaerythritol mayprovide for the making of a tetraester, thereby enabling formation ofstar or network-type copolymers. The tetraesters may be used ascomonomers with olefins to provide for viscosity index (VI) improvers.The tetraesters may be post-treated with polyamines, polyhydricalcohols, and/or alkali or alkaline-earth metal bases to providematerials with dispersant, detergent and/or fuel economy properties.

The functionalized polymer may be derived from one or more unsaturatedfatty esters, and subsequent to polymerization the polymer may betransesterified with one or more of the above-indicated alcohols orpolyols. For example, a functionalized polymer derived from methyl8-nonenoate, methyl 9-decenoate, methyl 10-undecenoate, methyl9-dodecenoate, methyl 9-octadecenoate, or a mixture of two or morethereof, may be transesterified with an alcohol and/or a polyol. Thealcohol may contain 2 to about 20 carbon atoms, or from 2 to about 12carbon atoms, or from 2 to about 8 carbon atoms, or from 2 to about 4carbon atoms, and may include ethanol, propanol, butanol, mixtures oftwo or more thereof, and the like. The polyol may contain from 2 toabout 10 carbon atoms, and from 2 to about 6 hydroxyl groups. Examplesmay include ethylene glycol, glycerol, trimethylolpropane,1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol,2,3-butanediol, 2-ethyl-1,3-propanediol,2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, pentaerythritol, sorbitol, mixtures oftwo or more thereof, and the like.

The functionalized polymer may comprise a homopolymer or oligomerwherein a single functionalized monomer is polymerized. Thefunctionalized polymer may comprise a copolymer or co-oligomer when twoor more functionalized monomers are copolymerized.

The functionalized polymer may comprise a copolymer or co-oligomerderived from one or more of the functionalized monomers and one or morecomonomers wherein from about 1 to about 99 mole percent, or from about5 to about 95 mole percent, or from about 5 to about 50 mole percent, orfrom about 5 to about 30 mole percent, of the repeating units arederived from the one or more functionalized monomers.

The functionalized polymer may comprise a copolymer or co-oligomercontaining structural repeating units derived from an ester selectedfrom methyl 8-nonenoate, methyl 9-decenoate, methyl 10-undecenoate,methyl 9-octadecenoate, or a mixture of two or more thereof; andstructural repeating units derived from an alpha olefin selected from1-octene, 1-decene, 1-dodecene, or a mixture of two or more thereof. Themolar ratio of ester to alpha olefin may range from about 10:1 to about1:10, or from about 5:1 to about 1:5, or from about 2:1 to about 1:2, orabout 1:1. The functionalized polymer may be hydrogenated. Thefunctionalized polymer may be used as a base oil for a lubricant orfunctional fluid. This base oil may be referred to as a functional baseoil. The polymerization reaction is illustrated below.

The functionalized polymer may be reacted with one or more enophilicreagents to form one or more enophilic reagent modified functionalizedpolymers. These may be referred to as polyfunctionalized polymers. Thisis described below.

The functionalized polymer may have any desired molecular weight, forexample, a number average molecular weight in the range from about 100to about 50,000 or more, or from about 300 to about 50,000, or fromabout 300 to about 20,000, or from about 300 to about 10,000, or fromabout 300 to about 5,000, or from about 500 to about 3000, as determinedby gel permeation chromatography (GPC), NMR spectroscopy, vapor phaseosometry (VPO), wet analytical techniques such as acid number, basenumber, saponification number or oxirane number, and the like. Thepolymer may comprise a homopolymer, copolymer, oligomer or aco-oligomer.

The functionalized polymer may be formed using conventionalpolymerization techniques. The polymerization process may comprise abatch process, a continuous process, or a staged process. Polymerizationmay be effected either via the one or more carbon-carbon double bonds,the functional groups and/or the additional functionality provided bythe enophilic reagent. Polymerization may be effected through acondensation reaction between one or more of the functionalizedmonomers, polyfunctionalized monomers, and/or comonomers. Thepolymerization may involve employing one or more cationic, free radical,anionic, Ziegler-Natta, organometallic, metallocene, or ring-openingmetathesis polymerization (ROMP) catalysts. Free radical initiators mayinclude azo compounds, peroxides, light (photolysis), and combinationsthereof. The azo compounds may include azobisisobutyronitrile (AlBN),1,1′-azobis(cyclohexanecarbonitrile), and the like, and combinationsthereof. The peroxide compounds may include benzoyl peroxide, methylethyl ketone peroxide, tert-butyl peroxide, di-tert-butylperoxide,t-butyl peroxy benzoate, di-t-amyl peroxide, lauroyl peroxide, dicumylperoxide, tert-butyl perpivalate, di-tert-amyl peroxide, dicetylperoxydicarbonate, tert-butyl peracetate,2,2-bis(tert-butylperoxy)butane,2,5-bis(tert-butylperoxy)-2,5-dimethyl-3-hexyne,2,5-bis(tert-butylperoxy)-2,5-dimethylhexane,2,5-dimethyl-2,5-di(t-butyl peroxy)hexane, and the like, andcombinations thereof. The free radical initiator may comprise di-t-butylperoxide. The anionic catalyst may include butyl lithium. Optionally, itmay be desirable to control the molecular weight and moleculararchitecture prior to or during polymerization by the addition of achain transfer agent. Suitable chain transfer agents may includedodecanethiol, t-nonylthiol, tetramethylsilane, cyclopropane, sulfurhexafluoride, methane, t-butanol, ethane, ethylene oxide,2,2-dimethylpropane, benzene, carbon tetrachloride, andbromotrichloromethane.

Polymerization may be achieved under cationic conditions and, in suchembodiments, the acid catalyst may comprise a Lewis Acid, a Brønstedacid, or a combination thereof. The Lewis acids may include BF₃, AlCl₃,zeolite, and the like, and complexes thereof, and combinations thereof.The Brønsted acids may include HF, HCl, H₂SO₄, phosphoric acid, acidclay, Amberlyst 15 (a product of Rohm and Haas identified as a sulfonicacid, macroreticular polymeric resin based on crosslinked styrenedivinylbenzene copolymers), trifluoromethanesulfonic acid (CF₃SO₃H),fluorosulfonic acid (FSO₃H), and the like, and combinations thereof.

Polymerization may be achieved using an olefin polymerization catalyst(e.g., BF₃) and a promoter (e.g., an alcohol) or a dual promoter (e.g.,an alcohol and an ester) as described U.S. Pat. Nos. 7,592,497 B2 and7,544,850 B2.

The catalysts described herein may be supported on a support. Forexample, the catalysts may be deposited on, contacted with, vaporizedwith, bonded to, incorporated within, adsorbed or absorbed in, or on,one or more supports or carriers. The catalysts described herein may beused individually or as mixtures. The polymerizations using multiplecatalysts may be conducted by addition of the catalysts simultaneouslyor in a sequence.

The functionalized polymer may comprise a mixture of different sizepolymers. Although the degree of polymerization (DP) of a polymer inaccordance with the present teachings is not restricted, it is to beunderstood that polymerization may result in mixtures of polymers havingdifferent DP values. The DP of the functionalized polymers may rangefrom about 2 to about 350. It is to be understood that some polymers inthe mixture may correspond to homopolymers of the functionalizedmonomers as well as to copolymers. The functionalized polymer, which maybe a homopolymer, copolymer, oligomer or co-oligomer, may have anydesired molecular weight depending on its intended use, for example, anumber average molecular weight in the range from about 100 to about50,000 or more, or from about 300 to about 50,000, or in the range fromabout 300 to about 25,000, or in the range from about 300 to about10,000 or in the range from about 500 and about 3000, as determined bygel permeation chromatography (GPC), spectroscopy; vapor phase osometry(VPO), wet analytical techniques such as acid number, base number,saponification number or oxirane number, and the like.

In an embodiment, the functionalized polymer may be represented by thefollowing structure:

wherein: R, R₁, and R₂ may be independently hydrogen, a C₁-C₂₂ alkyl, or—CH₂(CH₂)_(o)CH₂X. When R₁ and R₂ are alkyl groups, the total number ofcarbon atoms in these groups may be in the range from about 4 to about35 carbon atoms. X may be —OH, —NH₂, alkylamino, dialkylamino, or—CO₂R₃, wherein R₃ may be hydrogen or a C₁-C₁₀ alkyl group derived froma monohydric alcohol, polyhydric alcohol, amine, and/or polyalkylenepolyamine. m may be an integer from 0 to about 400. n may be an integerfrom 1 to about 300. m+n may be in the range from 1 to about 320. o maybe an integer from 1 to about 16. z may be an integer from 1 to about350.

The functionalized polymer may be combined with other polymers bymethods known to those skilled in the art. These may includepolyurethanes, polyacrylates, polyesters, silicones, and the like.

Adjuvants useful in the preparation of the functionalized polymer and/orin its subsequent use may be added during or subsequent to thepolymerization reaction. These may include surfactants, defoamers,leveling agents, antioxidants, thixotropic additives, plasticizers,preservatives, mixtures of two or more thereof, and the like.

Example 1

The following example discloses the oligomerization of 1-decene withmethyl 9-decenoate (which may be referred to as 9-DAME or 9-DAMe) in thepresence of di-t-amyl peroxide. The reaction proceeds according to thefollowing equation using the reagents shown in the table below.

1-decene 9-DAME di-t-amyl peroxide FW 140.27 184.28  174.28  equivalents 10.00  1.00* mol   0.8046   0.0805    0.1408** g 112.86 14.83 24.54 d(g/ml)  0.74  0.90  0.82 ml 152.3  16.5  30.00 Note: *9-DAME is 9.09 mol% of the total monomer mixture. **1.75X the “original” peroxide loadingThe following process steps are followed:

A 250 ml 3-necked round-bottomed flask, equipped with a magneticstirrer, inert gas inlet/outlet, rubber septum, thermocouple controlledheating mantle, and Dean-Stark trap with condenser, is charged with1-decene and 9-DAME. The monomer mixture is sparged with inert gas for 1hour to overnight.

After sparging, the monomer mixture is heated to 150° C. After reachingreaction temperature, the first 1/10 volume portion of peroxide is addedby syringe. Peroxide is added in 1/10 portions every 30 minutes (4.5hours total addition time).

After the initiator addition is complete, the reaction mixture isstirred at 150° C. for 4 hours (8 half lives for the peroxideinitiator), then heating is stopped and the reaction is allowed to coolto ambient temperature.

The completed reaction is stripped by equipping the three-neckround-bottom flask with a short path distillation head and receivingflask. With thermocouple controlled heating, the mixture is heatedslowly to 200° C. under vacuum. Stripping to 200-205° C. at <2 torrremoves the residual monomer to the target <0.25%. The pot residue isthe desired product.

The product is filtered while warm (at about 70 to 100° C.) using amedium coarseness paper filter or a coarse fritted filter.

The Dean-Stark trap is used to remove the low boiling point byproductsgenerated by decomposition of the initiator (e.g. alcohols, ketones).The reaction can be carried out without the trap; however, vigorousrefluxing occurs during the reaction, which can reduce the reactiontemperature due to evaporative cooling.

The monomers are sparged before heating and the reaction is carried outunder a blanket of inert gas.

The baseline, “original” level of peroxide is ˜8.3 mol % of the totalreaction mixture (mol peroxide/(mol peroxide+decene+9DAME)=0.0833).

Reaction of the Functionalized Monomers and/or Polymers with EnophilicReagents to Form Enophilic Reagent Modified Functionalized Monomersand/or Polymers

The functionalized monomer and/or polymer may be reacted with anenophilic reagent to form an enophilic reagent modified functionalizedmonomer and/or functionalized polymer. This may provide thefunctionalized monomers and polymers with additional levels offunctionality. These monomers and polymers may be referred to aspolyfunctionalized monomers and polymers. The enophilic reagent maycomprise an enophilic acid, anhydride and/or ester reagent (e.g., maleicanhydride), an oxidizing agent, an aromatic compound, a sulfurizingagent, hydroxylating agent, halogenating agent, or a mixture of two ormore thereof. The enophilic reagent may be reactive towards one or moreof the carbon-carbon double bonds in the functionalized monomer orpolymer.

The enophilic reagent modified functionalized monomer may be polymerizedto form an enophilic reagent modified functionalized polymer (oroligomer), or copolymerized with a comonomer to form an enophilicreagent modified functionalized copolymer (or co-oligomer). Thecomonomer may comprise an olefin, acrylic acid, acrylic acid ester,methacrylic acid, methacrylic acid ester, unsaturated polycarboxylicacid or derivative thereof, polyhydric alcohol, polyamine, polyalkylenepolyamine, isocyanate, diisocyanate, unsaturated nitrile, vinyl ester,vinyl ether, halogenated monomer, alkenyl-substituted aromatic compound(e.g., styrene), alkenyl-substituted heterocyclic compound,organosilane, or a mixture of two or more thereof. The comonomer maycomprise an olefin containing from 2 to about 30, or from about 6 toabout 24, carbon atoms per molecule. These are discussed above.

The polymerization procedure may be the same as discussed above. Thepolymerization procedure may comprise an acid- or base-catalyzedcondensation type polymerization. The polyfunctionalized monomers and/orpolymer (which may comprise a copolymer, an oligomer or co-oligomer) mayhave any desired molecular weight depending upon its intended use, forexample, a number average molecular weight in the range from about 100to about 50,000 or higher, or from about 300 to about 50,000, or fromabout 150 to about 20,000, or from about 200 to about 10,000, or fromabout 300 to about 5,000, or from about 500 to about 3000, as determinedby gel permeation chromatography (GPC), NMR spectroscopy, vapor phaseosmometry (VPO), wet analytical techniques such as acid number, basenumber, saponification number or oxirane number, and the like.

The ratio of the reactants in the reaction between the functionalizedmonomer or polymer and the enophilic reagent may be measured by theratio of the reaction equivalents of the monomer or polymer in thereaction to the reaction equivalents of the enophilic reagent in thereaction. The number of equivalents of the functionalized monomer orpolymer may be based on the number of carbon-carbon double bonds in themonomer or polymer. Thus, for example, one mole of a functionalizedmonomer having two carbon-carbon double bonds in its hydrocarbyl groupwould have an equivalent weight equal to one-half a mole of the monomer,if the reaction of both double bonds is intended. However, if thereaction of one double bond is intended, then the equivalent weight ofsuch a compound will be the same as its molecular weight. The numberaverage molecular weight of an equivalent of a functionalized polymerhaving an overall number average molecular weight of 1000 and fivecarbon-carbon double bonds in its molecular structure would be 200, 400,600, 800, and 1000; depending upon the number of double bonds takingpart in the reaction.

Enophilic Acid-Functionalized Derivative

The functionalized monomer or functionalized polymer of the inventionmay be reacted with an enophilic acid, anhydride and/or ester reagent toform an enophilic acid functionalized derivative. This derivative may bereferred to as a enophilic acid modified functionalized monomer orpolymer. When the enophilic acid reagent is maleic anhydride, thederivative may be referred to as a maleinated derivative.

The enophilic acid, anhydride and/or ester reagent may comprise one ormore unsaturated carboxylic acids and/or derivatives thereof. Thederivative may comprise one or more anhydrides or esters, or one or moreamides, aldehydes, acyl halides, and the like. The carboxylic acid orderivative may comprise one or more monobasic and/or polybasicunsaturated carboxylic acids or derivatives thereof. The monobasiccarboxylic acids may comprise one or more compounds represented by theformula

wherein R¹ and R² are independently hydrogen or hydrocarbyl groups. R¹and R² independently may be hydrocarbyl groups containing 1 to about 20carbon atoms, or from 1 to about 12 carbon atoms, or from 1 to about 4carbon atoms.

The polybasic carboxylic acid reagents may comprise one or more alpha,beta unsaturated dicarboxylic acids or derivatives thereof. These mayinclude those wherein a carbon-carbon double bond is in an alpha,beta-position to at least one of the carboxy functions (e.g., itaconicacid, or derivative thereof) or in an alpha, beta-position to both ofthe carboxy functions (e.g., maleic acid, anhydride or derivativethereof). The carboxy functions of these compounds may be separated byup to about 4 carbon atoms, or about 2 carbon atoms.

Examples of the enophilic acid, anhydride or esters, reagents mayinclude one or more of acrylic acid, methacrylic acid, cinnamic acid,crotonic acid, 3-phenyl propenoic acid, decenoic acid, maleic acid,fumaric acid, mesconic acid, itaconic acid, citraconic acid, and/oranhydrides of any of the foregoing acids including maleic anhydride,and/or esters of any of the foregoing acids and/or anhydrides, and/ormixtures of two or more thereof. The esters may be derived from any ofthe foregoing acids and/or anhydrides and one or more alcohols and/orone or more polyols. The alcohols may contain from 1 to about 18 carbonatoms, or from 1 to about 8 carbon atoms. The alcohols may includemethanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol,octanol, decanol, dodecanol, tetradecanol, hexadecanol, octadecanol,isopropanol, isobutanol, sec-butanol, tert-butanol, isopentanol, amylalcohol, isoamyl alcohol, neopentyl alcohol, tert-pentanol,cyclopentanol, cyclohexanol, 2-ethyl-hexanol, allyl alcohol, crotylalcohol, methylvinyl carbinol, benzyl alcohol, alpha-phenylethylalcohol, beta-phenylethyl alcohol, diphenylcarbinol, triphenylcarbinol,cinnamyl alcohol, mixtures of two or more thereof, and the like. Thepolyols may contain from 2 to about 10 carbon atoms, and from 2 to about6 hydroxyl groups. The polyols may include ethylene glycol, glycerol,trimethylolpropane, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 2,3-butanediol, 2-ethyl-1,3-propanediol,2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, pentaerythritol, sorbitol, mixtures oftwo or more thereof, and the like.

The ratio of equivalents of the functionalized monomer or functionalizedpolymer to equivalents the enophilic acid, anhydride and/or esterreagent may be from about 1 to about 4, or from about 1 to about 2. Theweight of an equivalent of an enophilic acid, anhydride and/or esterreagent is dependent on the number of carbon-carbon double bonds and/orreactive functional groups in its molecular structure. For example, onemole of an enophilic acid reagent having one carbon-carbon double bondin its molecular structure (e.g., maleic anhydride) would have anequivalent weight equal to its molecular weight, if the reaction waswith an olefin, commonly referred to as ene reaction. However, if maleicanhydride were used in an esterification reaction, its equivalent weightwould be one-half of its molecular weights. If the ene product, whichwould have a single carbon-carbon double bond, underwent another enereaction, its equivalent weight would be the same as its molecularweight.

The reaction between the functionalized monomer or functionalizedpolymer and the enophilic acid, anhydride and/or ester reagent may be athermal reaction conducted without a catalyst, or it may be a catalyticreaction. The catalyst may comprise a dialkylperoxide, or a Lewis acidsuch as AlCl₃. The reaction temperature (with or without a catalyst) maybe in the range from about 100° C. to about 300° C., or from about 150°C. to about 250° C.

The amount of catalyst added to the reaction may be from about 5 percentby weight to about 15 percent by weight of the functionalized monomer orfunctionalized polymer, or from about 5 percent by weight to about 10percent by weight.

The reaction may be conducted in an inert atmosphere, for example, anitrogen atmosphere. The time of reaction may range from about 1 toabout 24 hours, or from about 6 to about 12 hours.

Following the reaction, the product mixture may be subjected toisolation of the crude material. The crude material may be subjected toa vacuum to separate undesired volatile materials from the product.

The malienated derivative may comprise the product made by the reactionof maleic anhydride with one or more internal olefinic esters. The estermay comprise an alkene chain of from about 4 to about 30 carbon atoms,or from about 6 to about 24 carbon atoms, or from about 8 to about 18carbon atoms, or about 12 carbon atoms, and 1, 2 or 3 internalcarbon-carbon double bonds. The ester may comprise an alkene chain ofabout 12 carbon atoms with an internal carbon-carbon double bond. Themolar ratio of the maleic anhydride to the ester may range from about1:1 to about 2:1. This derivative may be further reacted with one ormore alcohols to provide one or more functional products (e.g.,polyester) which may be useful as functional base oils for lubricantsand functional fluids. The functional base oil may provide the lubricantor functional fluid with enhanced dispensency characteristics.

The malienated derivative may comprise the product made by the reactionof methyl 9-decenoate with maleic anhydride. The molar ratio of themaleic anhydride to methyl 9-decenoate may range from about 1:1 to about2:1. This derivative may be further reacted with one or more alcohols toprovide polyesters which may be useful as functional base oils forlubricants and functional fluids. This is discussed below.

Example 2

The following example discloses a process for the maleinization ofmethyl 9-decenoate (9-DAME). 9-DAME is reacted with maleic anhydride inan ene reaction to introduce one to two succinic groups per ester.Maleic anhydride is known to participate in ene reactions; this is dueto the combined electron-withdrawing power of the two carbonyl groupsadjacent to the double bond. The mechanism is believed to involve anallylic shift of one double bond by transferring the allylic hydrogen tothe enophile and generating a new bond. The reaction may be promoted byheat and/or Lewis acids. In this reaction no catalyst is used.

2532.9 g (13.74 mol) 9-DAME and 1684.8 g (17.18 mol, 1.25 eq) of maleicanhydride are added into a 5 L three neck flask equipped with a largeegg-shaped magnetic stirbar. The flask is then set into a heating mantel(two piece soft heating mantel with zipper). Two condensers areattached, one for incoming nitrogen gas and the other one for theoutgoing gas flow. The condensers are air cooled to prevent maleicanhydride to sublime into the gasline. The third neck is used for thethermocouple to control the temperature. After the maleic anhydride ismolten the stirrer is set to 750 rpm (two layers combine into one clearphase) and the temperature is stepwise increased to 200° C. The colorchanges during the reaction starting from colorless to yellow, orangeand then to dark red with increasing viscosity. The reaction is kept at200° C. for 6 hours. After the reaction mixture cools down to roomtemperature, a shortpath distillation bridge with ice cooled receivingflask is attached and high vacuum is applied starting at ambienttemperature and stepwise increasing the temperature up to 200° C. toadjust the distillate flow. Unreacted maleic anhydride distills first.Later at higher temperature it is a mixture of maleic anhydride andunreacted 9-DAME. The distillation is carried out until the distillateflow diminishes. The product is a viscous clear oil with a honey likeappearance. Small volumes show a golden color. Larger samples are morered. The yield is 3520 g (83.5%, reactor charge 4217.7 g) afterstripping. The acid value (AV) is determined for two samples using aMetrohm 848 Titrino Plus following USP 31: Sample 1 (0.367 g): AV 407.1mg KOH/g; and Sample 2 (0.265 g): AV 407.2 mg KOH/g. Dynamic viscostiesare measured at 40° C. and 100° C. using a RVDV3 Ultra with the resultsbeing: η=300 cP (40° C.); and η=22.5 cP (100° C.).

Example 3

The following example discloses a process for the maleinization of9-octadecenoic acid dimethyl ester (ODDA FAME). After filtration oversilica gel 1277.7 g (3.75 mol) of ODDA FAME are reacted with 441.5 g(4.50 mol, 1.2 eq) of maleic anhydride. After a reaction time of 6 hoursat 200° C. the product is stripped in high vacuum to remove unreactedmaleic anhydride. The product is a viscos, brown oil, which istransparent in smaller volumes. NMR shows no residual free maleicanhydride in the stripped product. The AV for the product is 233.8. Theconversion is 91.4%. The KV (cSt) at 100° C. is 17.32. The product maybe represented by the following formula:

Oxidized Derivative

The functionalized monomer or functionalized polymer of the inventionmay be reacted with one or more oxidizing agents. This may result in theformation of one or more oxidized derivatives which may be in the formof one or more epoxides. These may be referred to as polyfunctionalizedmonomers or polymers

The oxidizing agent may comprise any compound that provides oxygen atomsfor reaction with one or more of the carbon-carbon double bonds of thefunctionalized monomer or functionalized polymer. The oxidizing agentmay comprise any compound containing an oxygen-oxygen single bond, or aperoxide group or peroxide ion. Examples include hydrogen peroxide,organic peroxides such as peroxy acids (e.g., peroxy carboxylic acid)and organic hydroperoxides (e.g., cumene hydroperoxide), and inorganicperoxides such as peroxide salts (e.g., alkali metal or alkaline earthmetal peroxides) and acid peroxides (e.g., peroxymonosulfuric acid,peroxydisulfuric acid, and the like).

The ratio of equivalents of the functionalized monomer or functionalizedpolymer to equivalents of the oxidizing agent may be from about 3 toabout 1, or from about 2 to about 1. The weight of an equivalent of anoxidizing agent is dependent on the number of oxygen atoms in theoxidizing agent that are reactive with the carbon-carbon double bonds inthe functionalized monomer or polymer. For example, one mole of anoxidizing agent having one oxygen atom available for reaction with thecarbon-carbon double bonds in the functionalized monomer or polymerwould have an equivalent weight equal to a fraction of the molecularweight of the oxidizing agent, depending upon the number of carbon-,carbon double bonds in the molecule being oxidized.

The reaction between the functionalized monomer or functionalizedpolymer and the oxidizing agent may be carried out in the presence of acatalyst. The catalyst may comprise Amberlyst (polymer based catalystavailable from Rohm & Haas), Amberlite (ion exchange resin availablefrom Rohm & Haas), formic acid, acetic acid and/or sulfuric acid.

The reaction of the functionalized monomer or functionalized polymerwith the oxidizing agent may be enhanced by heating the reaction mixture(with or without a catalyst) to a temperature in the range from about30° C. to about 180° C., or from about 50° C. to about 70° C.

The amount of catalyst added to the reaction may be from about 5 percentby weight to about 25 percent by weight of the functionalized monomer orfunctionalized polymer in the reaction mixture, or from about 5 percentby weight to about 20 percent by weight.

The reaction may be conducted in an inert atmosphere, for example, anitrogen atmosphere, in a solvent or neat (without solvent). The time ofreaction may range from about 6 to about 24 hours, or from about 8 toabout 12 hours.

Following the reaction, the product mixture may be subjected toisolation of the crude material. The crude material may be subjected toa vacuum to separate undesired volatile materials from the product.

Alkylated Aromatic Compound

The functionalized monomer or functionalized polymer of the inventionmay be reacted with one or more aromatic compounds to form an alkylatedaromatic compound. These may be referred to as alkylation reactionswherein the functionalized monomer or polymer may be attached to thearomatic compound via one or more of the carbon-carbon double bonds inthe functionalized monomer or polymer. The product may be referred to asa polyfunctionalized monomer or polymer.

The aromatic compound may comprise any aromatic compound capable ofreacting with the functionalized monomer or polymer of the invention.The aromatic compound may comprise an aromatic, aliphatic-substitutedaromatic, or aromatic-substituted aliphatic compound. The aromaticcompound may comprise a substituted aromatic compound, that is, anaromatic compound containing one or more non-hydrocarbon groups such ashydroxyl, halo, nitro, amino, cyano, alkoxy, acyl, epoxy, acryloxy,mercapto, mixtures of two or more thereof, and the like. The aromaticcompound may comprise a hetero substituted aromatic compound, that is,an aromatic compound containing one or more atoms other than carbon in achain or ring otherwise comprising carbon atoms; examples of such heteroatoms including nitrogen, oxygen and sulfur.

The aromatic compound may comprise one or more of benzene, naphthalene,naphthacene, alkylated derivatives thereof, and the like. The aromaticcompound may contain from 6 to about 40 carbon atoms, or from 6 to about30 carbon atoms, or from 6 to about 20 carbon atoms, or from 6 to about15 carbon atoms, or from 6 to about 12 carbon atoms. Examples mayinclude benzene, toluene, ethylbenzene, styrene, alpha-methyl styrene,propylbenzene, xylene, mesitylene, methylethylbenzene, naphthalene,anthracene, phenanthrene, methylnaphthalene, dimethylnaphthalene,tetralin, mixtures of two or more thereof, and the like. The aromaticcompound may comprise phenol and/or its derivatives, dihydroxybenzene,naphthol and/or dihydroxynaphthalene. The aromatic compound may comprisean aromatic amine and/or a pyridine. The aromatic compound may compriseaniline, diphenylamine, toluidine, phenylenediamine, diphenylamine,alkyldiphenylamine, and/or phenothiazine. The aromatic compound maycomprise an alkylbenzene with a multi-substituted benzene ring, examplesincluding o-, m- and p-xylene, toluene, tolyl aldehyde, toluidine, o-,m- and p-cresol, phenyl aldehyde, mixtures of two or more thereof, andthe like.

The ratio of equivalents of the functionalized monomer or polymer toequivalents of the aromatic compound may be from about 4:1 to about 1:1,or from about 2:1 to about 1:1. The weight of an equivalent of anaromatic compound would be equal to the molecular weight of the aromaticcompound, if only a single carbon-carbon double bond were to take partin the reaction. Otherwise, it would be a fraction of 1 (i.e., less than1).

The reaction between the functionalized monomer or polymer and thearomatic compound may be carried out in the presence of a catalyst. Thecatalyst may comprise a Lewis acid, Bronsted acid, acid clay and/orzeolite.

The reaction of the functionalized monomer or polymer with the aromaticcompound may be enhanced by heating the reaction mixture (with orwithout a catalyst) to a temperature in the range from about 50° C. toabout 300° C., or from about 100° C. to about 200° C.

The amount of catalyst added to the reaction may be from about 1 percentby weight to about 100 percent by weight of the functionalized monomeror polymer in the reaction mixture, or from about 30 percent by weightto about 50 percent by weight.

The reaction may be conducted in an inert atmosphere, for example, anitrogen atmosphere. The time of reaction may range from about 2 toabout 24 hours, or from about 6 to about 12 hours.

Following the reaction, the product mixture may be subjected toisolation of the crude material. The crude material may be subjected toa vacuum to separate undesired volatile materials from the product.

Sulfurized Derivative

The functionalized monomer or polymer of the invention may be reactedwith one or more sulfurizing agents to form a sulfurized derivative. Thesulfurized derivative may be referred to as a polyfunctionalized monomeror polymer.

The sulfurizing agent may comprise elemental sulfur and/or any suitablesulfur source. The sulfur source may comprise a variety of materialscapable of supplying sulfur to the reaction. Examples of useful sulfursources may include sulfur halides, combinations of sulfur or sulfuroxides with hydrogen sulfide, and various sulfurized organic compoundsas described below. The sulfur halides may include sulfur monochloride,sulfur dichloride, mixtures thereof, and the like. Combinations ofsulfur and sulfur oxides (such as sulfur dioxide), with hydrogen sulfidemay be used.

The sulfurizing agent may comprise one or more of the sulfur-coupledcompounds. These may include one or more sulfur-coupled organiccompounds, for example, disulfides (RSSR), trisulfides (RS₃R),polysulfides (RS_(x)R, where x is from 4 to 7), mixtures of two or morethereof, and the like.

The sulfurizing agent may comprise one or more phosphorus sulfides.Examples may include P₂S₅, P₄S₁₀, P₄S₇, P₄S₃ and P₂S₃, mixtures of twoor more thereof, and the like.

The sulfurizing agent may comprise one or more aromatic and/or alkylsulfides such as dibenzyl sulfide, dixylyl sulfide, dicetyl sulfide,diparaffin wax sulfide and/or polysulfide, cracked wax oleum sulfides,mixtures of two or more thereof, and the like. The aromatic and alkylsulfides may be prepared by the condensation of a chlorinatedhydrocarbon with an inorganic sulfide whereby the chlorine atom fromeach of two molecules may be displaced, and the free valence from eachmolecule may be joined to a divalent sulfur atom. The reaction may beconducted in the presence of elemental sulfur.

Dialkenyl sulfides that may be used may be prepared by reacting anolefinic hydrocarbon containing from about 3 to about 12 carbon atomswith elemental sulfur in the presence of zinc or a similar metalgenerally in the form of an acid salt. Examples of sulfides of this typemay include 6,6′-dithiobis(5-methyl-4-nonene), 2-butenyl monosulfide anddisulfide, and 2-methyl-2-butenyl monosulfide and disulfide.

Sulfurized olefins which may be used as the sulfurizing agent mayinclude sulfurized olefins prepared by the reaction of an olefin ofabout 3 to about 6 carbon atoms, or a lower molecular weight polyolefinderived therefrom, with a sulfur-containing compound such as sulfur,sulfur monochloride, sulfur dichloride, hydrogen sulfide, mixtures oftwo or more thereof, and the like.

The sulfurizing agent may comprise one or more sulfurized oils which maybe derived from one or more natural or synthetic oils including mineraloils, lard oil, carboxylic acid esters derived from aliphatic alcoholsand fatty acids or aliphatic carboxylic acids (e.g., myristyl oleate andoleyl oleate), sperm whale oil and synthetic sperm whale oilsubstitutes, and synthetic unsaturated esters or glycerides. Sulfurizedmineral oils may be obtained by heating a suitable mineral oil with fromabout 1 to about 5% by weight of sulfur at a temperature in the rangefrom about 175° C. to about 260° C. The mineral oils sulfurized in thismanner may be distillate or residual oils obtained from paraffinic,naphthenic or mixed base crudes. Sulfurized fatty oils such as asulfurized lard oil may be obtained by heating lard oil with about 10 to15% of sulfur at a temperature of about 150° C. for a time sufficient toobtain a homogeneous product.

The sulfurized fatty acid esters may be prepared by reacting sulfur,sulfur monochloride, and/or sulfur dichloride with an unsaturated fattyester at elevated temperatures. Typical esters may include C₁-C₂₀ alkylesters of C₈-C₂₄ unsaturated fatty acids such as palmitoleic, oleic,ricinoleic, petroselic, vaccenic, linoleic, linolenic, oleostearic,licanic, etc. Sulfurized fatty acid esters prepared from mixedunsaturated fatty acid esters such as those that may be obtained fromanimal fats and vegetable oils such as tall oil, linseed oil, olive oil,castor oil, peanut oil, rapeseed oil, fish oil, sperm oil, etc. also maybe used. Specific examples of the fatty esters which may be sulfurizedmay include methyl oleate, ethyl oleate, lauryl oleate, cetyl oleate,cetyl linoleate, lauryl ricinoleate, oleyl linoleate, oleyl stearate,alkyl glycerides, mixtures of two or more thereof, and the like.

Another class of organic sulfur-containing compounds which may be usedas the sulfurizing agent may include sulfurized aliphatic esters ofolefinic mono- or dicarboxylic acids. For example, aliphatic alcohols offrom 1 to about 30 carbon atoms may be used to esterify monocarboxylicacids such as acrylic acid, methacrylic acid; 2,4-pentadienoic acid,fumaric acid, maleic acid, muconic acid, etc. Sulfurization of theseesters may be conducted with elemental sulfur, sulfur monochlorideand/or sulfur dichloride.

Another class of sulfurized organic compounds which may be used as thesulfurizing agent may include diestersulfides represented by the formula

S_(y)((CH₂)_(x)COOR)₂

wherein x is a number in the range of about 2 to about 5; y is a numberin the range of 1 to about 6, or 1 to about 3; and R is an alkyl grouphaving from about 4 to about 20 carbon atoms. The R group may be astraight chain or branched chain group. Typical diesters may include thebutyl, amyl, hexyl, heptyl, octyl, nonyl, decyl, tridecyl, myristyl,pentadecyl, cetyl, heptadecyl, stearyl, lauryl, and eicosyl diesters ofthiodialkanoic acids such as propionic, butanoic, pentanoic and hexanoicacids. The diester sulfides may include dilauryl 3,3′-thiodipropionate.

The sulfurizing agent may comprise one or more sulfurized olefins. Thesemay include the organic polysulfides which may be prepared by thesulfochlorination of olefins containing four or more carbon atoms andfurther treatment with inorganic higher polysulfides according to U.S.Pat. No. 2,708,199.

The sulfurized olefins may be produced by (1) reacting sulfurmonochloride with a stoichiometric excess of a low carbon atom olefin,(2) treating the resulting product with an alkali metal sulfide in thepresence of free sulfur in a mole ratio of no less than 2:1 in analcohol-water solvent, and (3) reacting that product with an inorganicbase. This procedure is described in U.S. Pat. No. 3,471,404. The olefinreactant may contain from about 2 to about 5 carbon atoms. Examples mayinclude ethylene, propylene, butylene, isobutylene, amylene, andmixtures of two or more thereof. In the first step, sulfur monochloridemay be reacted with from one to two moles of the olefin per mole of thesulfur monochloride. The reaction may be conducted by mixing thereactants at a temperature of from about 20° C. to 80° C. In the secondstep, the product of the first step may be reacted with an alkali metal,preferably sodium sulfide, and sulfur. The mixture may comprise up toabout 2.2 moles of the metal sulfide per gram atom of sulfur, and themole ratio of alkali metal sulfide to the product of the first step maybe about 0.8 to about 1.2 moles of metal sulfide per mole of step (1)product. The second step may be conducted in the presence of an alcoholor an alcohol-water solvent under reflux conditions. The third step ofthe process may comprise the reaction between the phosphosulfurizedolefin which may contain from about 1 to about 3% of chlorine with aninorganic base in a water solution. Alkali metal hydroxide such assodium hydroxide may be used. The reaction may be continued until thechlorine content is reduced to below about 0.5%. This reaction may beconducted under reflux conditions for a period of from about 1 to about24 hours.

The sulfurizing agent may be prepared by the reaction, undersuperatmospheric pressure, of olefinic compounds with a mixture ofsulfur and hydrogen sulfide in the presence of a catalyst, followed byremoval of low boiling materials. This procedure is described in U.S.Pat. No. 4,191,659. An optional final step described in this patent isthe removal of active sulfur by, for example, treatment with an alkalimetal sulfide. The olefinic compounds which may be sulfurized by thismethod may contain at least one carbon-carbon double bond. Thesecompounds may be represented by the formula

R¹R²C═CR³R⁴

wherein each of R¹, R², R³ and R⁴ is hydrogen or a hydrocarbyl group.Any two of R¹, R², R³ and R⁴ may together form an alkylene orsubstituted alkylene group; i.e., the olefinic compound may bealicyclic.

The ratio of equivalents of the functionalized monomer or polymer toequivalents of the sulfurizing agent may be from about 1 to about 10, orfrom about 1 to about 6. The weight of an equivalent of a sulfurizingagent is dependent on the number of sulfur atoms in the sulfurizingagent that are reactive with the carbon-carbon double bonds in thefunctionalized monomer or polymer. For example, one mole of asulfurizing agent having one sulfur atom available for reaction with thecarbon-carbon double bonds in the functionalized monomer or polymerwould have an equivalent weight equal to the molecular weight of thesulfurizing agent.

The reaction between the functionalized monomer or polymer and thesulfurizing agent may be carried out in the presence of a catalyst. Thecatalyst may comprise tertiary phosphine, iodine, BF₃, metaldithiocarbamate, and the like.

The reaction of the functionalized monomer or polymer with thesulfurizing agent may be enhanced by heating the reaction mixture (withor without a catalyst) to a temperature in the range from about 130° C.to about 200° C., or from about 150° C. to about 180° C.

The amount of catalyst added to the reaction may be from about 1 percentby weight to about 20 percent by weight of the functionalized monomer orpolymer, or from about 5 percent by weight to about 10 percent byweight.

The reaction may be conducted in an inert atmosphere, for example, anitrogen atmosphere. The time of reaction may range from about 2 toabout 8 hours, or from about 4 to about 6 hours.

Following the reaction, the product mixture may be subjected toisolation of the crude material. The crude material may be subjected toa vacuum to separate undesired volatile materials from the product.

Hydroxylated Derivative

The functionalized monomer or polymer of the invention may be reactedwith one or more hydroxylating agents to form a hydroxylated derivative.The hydroxylated derivative may be referred to as a polyfunctionalizedmonomer or polymer.

The hydroxylation agent may comprise any compound that introduces ahydroxyl into the monomer or polymer. The hydroxylating agent maycomprise water, hydrogen peroxide, or a mixture thereof.

The ratio of equivalents of the functionalized monomer or polymer toequivalents of the hydroxylating agent may be from about 1 to about 8,or from about 1 to about 4. The weight of an equivalent of anhydroxylating agent is dependent on the number of hydroxyl groups in thehydroxylating agent that are reactive with the carbon-carbon doublebonds in the functionalized monomer or polymer. For example, one mole ofan hydroxylating agent having one hydroxyl group available for reactionwith each carbon-carbon double bond in the functionalized monomer orpolymer would have an equivalent weight equal to the molecular weight ofthe hydroxylating agent.

The reaction between the functionalized monomer or polymer and thehydroxylating agent may be carried out in the presence of a catalyst.The catalyst may comprise oxygen, or a strong mineral acid such ashydrochloric acid, sulfuric acid, hydroiodic acid, or a mixture of twoor more thereof.

The reaction of the functionalized monomer or polymer with thehydroxylating agent may be enhanced by heating the reaction mixture(with or without a catalyst) to a temperature in the range from about20° C. to about 100° C., or from about 25° C. to about 60° C.

The amount of catalyst added to the reaction may be from about 1 percentby weight to about 20 percent by weight of the functionalized monomer orpolymer in the reaction mixture, or from about 5 percent by weight toabout 10 percent by weight. The time of reaction may range from about 2to about 12 hours, or from about 3 to about 5 hours.

Following the reaction, the product mixture may be subjected toisolation of the crude material. The crude material may be subjected toa vacuum to separate undesired volatile materials from the product.

Halogenated Derivative

The functionalized monomer or polymer of the invention may be reactedwith one or more halogenating agents to form a halogenated derivative.The halogenated derivative may be referred to as a polyfunctionalizedmonomer or polymer.

The halogenating agent may comprise any compound that provides for theaddition of a halogen atom (e.g., F, Cl, Br, I, or a mixture of two ormore thereof) to the monomer or polymer. The halogenating agent maycomprise fluorine, chlorine, bromine, iodine, hydrogen chloride,hydrogen bromide, hydrogen fluoride, iodine monochloride, antimonypentafluoride, molybdenum pentachloride, nitrogen fluoride oxide,antimony pentachloride, tungsten hexafluoride, tellurium hexafluoride,sulfur tetrafluoride, sulfur monochloride, silicon tetrafluoride,phosphorus pentafluoride, or a mixture of two or more thereof.

The ratio of equivalents of the functionalized monomer or polymer toequivalents of the halogenating agent may be from about 1 to about 8, orfrom about 1 to about 4. The weight of an equivalent of a halogenatingagent is dependent on the number of halogen atoms in the halogenatingagent that are reactive with each carbon-carbon double bond in thefunctionalized monomer or polymer. For example, one mole of ahalogenating agent having one halogen atom available for reaction withthe carbon-carbon double bonds in the functionalized monomer or polymerwould have an equivalent weight equal to the molecular weight of thehalogenating agent.

The reaction between the functionalized monomer or polymer and thehalogenating agent may be carried out in the presence of a catalyst. Thecatalyst may comprise light, oxygen, one or more peroxides, one or moremetal halides, or a mixture of two or more thereof.

The reaction of the functionalized monomer or polymer with thehalogenating agent may be enhanced by heating the reaction mixture (withor without a catalyst) to a temperature in the range from about 20° C.to about 100° C., or from about 40° C. to about 60° C.

The amount of catalyst added to the reaction may be from about 2 percentby weight to about 10 percent by weight of the functionalized monomer orpolymer in the reaction mixture, or from about 3 percent by weight toabout 5 percent by weight. The time of reaction may range from about 1to about 12 hours, or from about 2 to about 6 hours.

Following the reaction, the product mixture may be subject to isolationof the crude material. The crude material may be subjected to a vacuumto separate undesired volatile materials from the product.

Derivatized Functionalized Compounds

The functionalized or polyfunctionalized monomers and/or polymers, orenophilic reagent modified functionalized monomers and/or polymers, ofthe invention may be further derivatized by reaction with one or moreoxygen-containing reagents (e.g., alcohols, polyols, etc.), one or morenitrogen-containing reagents (e.g., ammonia, amines, polyamines,aminoalcohols, amine terminated polyoxyalkylenes, etc.), metals, metalcompounds, or a mixture of two or more thereof, to form one or morederivatized functionalized compounds. These compounds may compriseesters, di-esters, tri-esters, amides, di-amides, triamides, imides,amide esters, amine salts, ammonium salts, ester salts, metal salts,mixtures of two or more thereof, and the like.

The polyfunctionalized monomers and/or polymers may comprise malienatedfunctionalized monomers and/or polymers, including malienated methyl8-nonenoate, malienated methyl 9-decenoate, malienated methyl10-undecenoate, malienated methyl 9-dodecenoate, malienated dimethylesters of 9-octadecenoic acid, mixtures of two or more thereof, and thelike.

The metal may be an alkali metal (e.g., a Group IA metal such as Li, Na,K, Rb, and Cs); alkaline earth metal (e.g., Group IIA metals such as Be,Mg, Ca, Sr, and Ba); Group IIIA metal (e.g., B, Al, Ga, In, and Tl);Group IVA metal (e.g., Sn and Pb), Group VA metal (e.g., Sb and Bi),transition metal (e.g., Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Mo,Ru, Rh, Pd, Ag and Cd), lanthanide or actinides, or a mixture of two ormore thereof. The metal may comprise an alkali metal, alkaline earthmetal, titanium, zirconium, molybdenum, iron, copper, aluminum, zinc, ora mixture of two or more thereof.

The nitrogen-containing reagent may comprise ammonia and/or a compoundcontaining one or more primary and/or secondary amino groups. These maybe referred to as amines. The amine may be a monoamine or a polyamine.The amine may be a mono-substituted amine having one non-hydrogensubstituted group (such as an alkyl, aryl group, alkyl-amino group, oraryl-amino group), a di-substituted amine having two non-hydrogensubstituted groups, an amino-alcohol, an amine terminatedpoly(oxyalkylene) or a combination of two or more thereof.

The mono-substituted and di-substituted amines may include methylamine,dimethylamine, ethylamine, diethylamine, propylamine, dipropylamine,butylamine, dibutylamine, pentylamine, dipentylamine, hexylamine,dihexylamine, heptylamine, diheptylamine, octylamine, dioctylamine, or amixture thereof. In other non-limiting embodiments, the amine is anamino-alcohol such as: methanolamine, dimethanolamine, ethanolamine,diethanolamine, propanolamine, dipropanolamine, butanolamine,dibutanolamine, pentanolamine, dipentanolamine, hexanolamine,dihexanolamine, heptanolamine, diheptanolamine, octanolamine,dioctanolamine, aniline, or a mixture of two or more thereof.

The amine may be a diamine. Examples may include ethylenediamine(1,2-ethanediamine), 1,3-propanediamine, 1,4-butanediamine(putrescine),1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine,1,8-octanediamine, 1,3-bis(aminomethyl)cyclohexane, meta-xylenediamine,1,8-naphthalenediamine, p-phenylenediamine,N-(2-aminoethyl)-1,3-propanediamine, or a mixture of two or morethereof.

The amine may be a triamine, a tetramine, or a mixture thereof. Examplesof these may include diethylenetriamine, dipropylenetriamine,dibutylenetriamine, dipentylenetriamine, dihexylenetriamine,diheptylenetriamine, dioctylenetriamine, spermidine, melamine,triethylenetetramine, tripropylenetetramine, tributylenetetramine,tripentylenetetramine, trihexylenetetramine, triheptylenetetramine,trioctylenetetramine, hexamine, or a mixture of two or more thereof. Theamine may be an imidazole, such as aminopropylimidazole, or anoxazolidine.

The amine may comprise ethanolamine, diethanolamine, diethylamine,ethylenediamine, hexamethyleneamine, or a mixture of two or morethereof. The amine may be ethylenediamine. The amine may bediethanolamine.

The amine may comprise an amino-alcohol. Examples may includemethanolamine, dimethanolamine, ethanolamine, diethanolamine,propanolamine, dipropanolamine, butanolamine, dibutanolamine,pentanolamine, dipentanolamine, hexanolamine, dihexanolamine,heptanolamine, diheptanolamine, octanolamine, dioctanolamine, aniline,or a mixture of two or more thereof.

The amine may comprise a polyamine or polyalkylene polyamine representedby the formula

wherein each R is independently hydrogen, a hydrocarbyl group or ahydroxy-substituted hydrocarbyl group containing up to about 30 carbonatoms, or up to about 10 carbon atoms, with the proviso that at leastone R is hydrogen, n is a number in the range from 1 to about 10, orfrom about 2 to about 8, and R¹ is an alkyene group containing 1 toabout 18 carbon atoms, or 1 to about 10 carbon atoms, or from about 2 toabout 6 carbon atoms. Examples of these polyamines may include methylenepolyamine, ethylene polyamine, propylene polyamine, butylenes polyamine,pentylene polyamine, hexylene polyamine, heptylene polyamine, ethylenediamine, triethylene tetramine, tris(2-aminoethyl)amine, propylenediamine, trimethylene diamine, hexamethylene diamine, decamethylenediamine, octamethylene diamine, di(heptamethylene)triamine, tripropylenetetramine, tetraethylene pentamine, trimethylene diamine, pentaethylenehexamine, di(trimethylene)triamine,2-heptyl-3-(2-aminopropyl)imidazoline, 1,3-bis(2-amino-ethyl)piperazine,1,4-bis(2-aminoethyl)piperazine, 2-methyl-1-(2-aminobutyl)piperazine, ora mixture of two or more thereof.

The amine may comprise one or more amine terminated poly(oxyalkylenes).These may include one or more alpha omega diaminopoly(oxyalkylenes). Theamine terminated, or alpha omega diamino terminated, poly(oxyalkylenes)may include amine terminated poly(oxyethylenes), amine terminatedpoly(oxypropylenes), amine terminatedpoly(oxyethylene)poly(oxypropylenes), amine terminatedpoly(oxypropylene)poly(oxyethylene)poly(oxyprolyene)s, mixtures of twoor more thereof, and the like. The amine terminated polyoxyalkylenes maycomprise urea condensates of such alpha omega diaminopoly(oxyethylene)s, alpha omega diaminopoly(oxypropylene)poly(oxyethylene)poly(oxypropylene)s, or alpha omegadiamino propylene oxide cappedpoly(oxypropylene)poly(oxyethylene)poly(oxypropylene)s, or alpha omegadiamino propylene oxide capped poly(oxyethylene)s. The amine terminatedpolyoxyalkylene may be a polyamine (e.g., triamino, tetramino, etc.)polyoxyalkylene. In the compounds that contain both poly(oxyethylene)and poly(oxypropylene) groups, the poly(oxyethylene) groups may dominateif water solubility is desired. The terminal amines may be primaryamines, e.g., —NH₂, or secondary amines, e.g. —NHR* wherein R* is ahydrocarbyl group of from 1 to about 18 carbon atoms, or from 1 to about4 carbon atoms. R* may be an alkyl or an alkenyl group. These compoundsmay have number average molecular weights of at least about 1000, or inthe range of about 1000 to about 30,000, or in the range of about 2000to about 10,000, or in the range of about 3500 to about 6500. Mixturesof two or more of these compounds may be used.

The equivalent ratio of C═O in the functionalized or polyfunctionalizedmonomer or polymer to N in the nitrogen-containing reagent may be fromabout 1 to about 10, or from about 1 to about 5.

The reaction between the functionalized or polyfunctionalized monomer orpolymer and the nitrogen-containing reagent may be carried out in thepresence of a catalyst. The catalyst may be a basic catalyst. Thecatalyst may comprise one or more of sodium carbonate, lithiumcarbonate, sodium methanolate, potassium hydroxide, sodium hydride,potassium butoxide, potassium carbonate, or a mixture thereof. Thecatalyst may be added to the reaction mixture in dry form or in the formof a solution. The reaction may be enhanced by heating the reactionmixture (with or without a catalyst) to at least about 80° C., or atleast 100° C., or at least about 120° C., or at least about 140° C., orat least about 160° C.

The amount of catalyst added to the reaction may be in the range fromabout 0.01 percent by weight to about 5 percent by weight of thefunctionalized or polyfunctionalized monomer or polymer, in the reactionmixture, or from about 0.01 percent by weight to about 1 percent byweight, or from about 0.2 percent by weight to about 0.7 percent byweight.

The reaction may be conducted in an inert atmosphere, for example, anitrogen atmosphere. The time of reaction may range from about 1 toabout 24 hours, or from about 1 to about 12 hours, or from about 1 toabout 6 hours, or from about 1 to about 4 hours.

The product may comprise one or more amides, di-amides, tri-amides,amide esters, imides, amine salts, ammonium salts, mixtures of two ormore thereof, and the like.

The oxygen-containing reagent may comprise one or more alcohols and/orone or more polyols. The alcohols may contain from 1 to about 18 carbonatoms, or from 1 to about 8 carbon atoms. These may include methanol,ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol,decanol, dodecanol, tetradecanol, hexadecanol, octadecanol, isopropanol,isobutanol, sec-butanol, tert-butanol, isopentanol, amyl alcohol,isoamyl alcohol, neopentyl alcohol, 2-ethyl-1-hexanol, tert-pentanol,cyclopentanol, cyclohexanol, allyl alcohol, crotyl alcohol, methylvinylcarbinol, benzyl alcohol, alpha-phenylethyl alcohol, beta-phenylethylalcohol, diphenylcarbinol, triphenylcarbinol, cinnamyl alcohol, mixturesof two or more thereof, and the like.

The polyols may contain from 2 to about 10 carbon atoms, and from 2 toabout 6 hydroxyl groups. Examples may include ethylene glycol, glycerol,trimethylolpropane, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 2,3-butanediol, 2-ethyl-1,3-propanediol,2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, pentaerythritol, sorbitol, mixtures oftwo or more thereof, and the like.

The equivalent ratio of C═O in the functionalized or polyfunctionalizedmonomer or polymer to —OH in the oxygen-containing reagent may be fromabout 1, to about 6, or from about 1 to about 3, or from about 1 toabout 2, or about 1.

The reaction between the functionalized or polyfunctionalized monomer orpolymer and the oxygen-containing reagent may be carried out in thepresence of a catalyst. The catalyst may be a Lewis acid, a Bronstedacid and/or a sulfonic acid. The reaction may be enhanced by heating thereaction mixture (with or without a catalyst) to a temperature in therange from about 100° C. to about 250° C., or from about 150° C. toabout 200° C.

The amount of catalyst added to the reaction may be from about 0.01percent by weight to about 5 percent by weight of the functionalized orpolyfunctionalized monomer or polymer in the reaction mixture, or fromabout 0.5 percent by weight to about 2 percent by weight.

The reaction may be conducted in an inert atmosphere, for example, anitrogen atmosphere. The time of reaction may range from about 3 toabout 24 hours, or from about 8 to about 12 hours.

The product may comprise one or more mono-, di- and/or tri-esters. Theproduct may comprise one or more polyesters which may be useful as baseoils for lubricants and functional fluids. These base oils may providethe lubricant or functional fluid with enhanced disperency properties,and as such may be referred to as functional base oils.

The following drawings are provided to disclose useful esterificationreactions for malienated methyl 9-decenoate (9-DAMe, which may also bereferred to as 9-DAME). In the drawings, the following abbreviations areused: 9-DAMe for methyl 9-decenoate; 9-DDAMe for methyl 9-dodecenoate;10-UDAMe for methyl 10-undecenoate; FAMe for fatty acid methyl ester;and 9-ODDA Me₂ for di-methyl ester 9-octadecenoic acid.

The following equations illustrate the preparation of polyhydric alcohol(i.e., polyol) esters of malienated methyl 9-decenoate (9-DAMe).

Example 4A

A lubricant composition is prepared that contains a maleinated 9-DAMEreacted with iso-amyl alcohol, which is then blended with apolyalphaolefin (PAO) 4 cSt, and additized with 0.5 w % of hindered arylamine and 0.5 w % of a polyisobutenyl succinic anhydride (PIBSA) baseddispersant with a 25 total base number (TBN). The preparation of theester is shown above.

Example 4B

Maleinized methyl 9-decenoate (MA9-DAMe) is reacted with severalmonofunctional alcohols in different ratios to produce half- and fullyconverted esters. Methanesulfonic acid (MSA) is used as catalyst. Thereactions are carried out solvent-free under nitrogen. All alcoholratios are calculated based on the acid value (AV) of the maleinizedstarting material. Reaction of the succinic anhydride of MA9-DAMe withhalf an equivalent of alcohol gives half esters, no water as byproductis generated. Alcohol ratios higher than 50% of the AV of the maleinized9-DAMe generate water from the condensation reaction. The reactionmixtures are heated for several hours. Reaction temperature is limitedby the boiling point of the alcohol. Water is allowed to evaporateduring heating. After the reaction the products are stripped in vacuumto remove additional water, residual free alcohols, and other volatiles.

Acid Kinematic Pour Point Alcohol Value Conversion Visclsity (ASTM D97)Isoamyl 2 93 6.0 cSt/100° C. −35° C. alcohol 1.2 eq Neat syntheticlubricant KV100 = 6 mm²/s CCS (−30° C.) = 5000 mPa · s Blended lubricantwith 79 w % derivative, 20% w 4 cSt PAO, 0.5 w % hinder aryl amine, 0.5w % PIBSA based succinimide dispersant. This blend has improved KV andCCS for use as a PCMO high fuel economy oil. KV100 = 4.336 mm²/s CCS(−30° C.) = 1520 mPa · s.

Example 4C

Maleinized methyl 9-decenoate (MA9-DAMe) is reacted with severalmonofunctional alcohols in different ratios to produce half- and fullyconverted esters. Methanesulfonic acid (MSA) is used as catalyst. Thereactions are carried out solvent-free under nitrogen. All alcoholratios are calculated based on the acid value (AV) of the maleinizedstarting material. Reaction of the succinic anhydride of MA9-DAMe withhalf an equivalent of alcohol gives half esters, no water as byproductis generated. Alcohol ratios higher than 50% of the AV of the maleinized9-DAMe generate water from the condensation reaction. The reactionmixtures are heated for several hours. Reaction temperature is limitedby the boiling point of the alcohol. Water is allowed to evaporateduring heating. After the reaction the products are stripped in vacuumto remove additional water, residual free alcohols, and other volatiles.

a) Isobutyl Alcohol

Isobutyl alcohol is reacted in 4 different ratios with maleinized9-DAMe. The low boiling point (bp 107.9° C.) of isobutyl alcohol makesit difficult to target exact conversions between half- and fullyconverted esters. Water cannot be removed by distillation during thereaction. To achieve high conversion an excess of isobutyl alcohol isused in one of the samples; see the table below. The equations belowshow the synthesis of the isobutyl half- and full-esters of maleinized9-DAMe.

b) 2-Ethyl-1-hexanol

2-Ethyl-1-hexanol has a boiling point of 183-185° C. Esters in differentratios are synthesized. The data in the table below show an AV for theequal ratio sample. An AV of around 10-15 units is generated from theresidual acid catalyst, which is not removed. Using a small excess(0.1-0.2 eq) of 2-ethyl-1-hexanol gives a more complete ester formation.The following equations show the synthesis of the 2-ethyl-1-hexanolhalf- and full-esters of maleinized 9-DAMe.

c) Isoamyl Alcohol

Due to the lower boiling point of isoamyl alcohol (bp 131° C.), anexcess of alcohol is used to drive the ester formation closer tocompletion. The following equations show the synthesis of the isoamylhalf- and full-esters of maleinized 9-DAMe.

d) Neopentyl Alcohol

Esterification with neopentyl alcohol to obtain a full ester is carriedout. The synthesis of the neopentyl alcohol ester of maleinized 9-DAMeis shown below.

The following table provides data for esters synthesized from maleinized9-DAMe:

η η KV**⁾ Sample Ester*⁾ (40° C.), (100° C.), (100° C.), PP ID AlcoholAV in % cP cP cSt (° C.) 1 Isobutanol, 88.2 82 125 15 12.42 1.0 eq 2Isobutanol, 77.8 60 435 30 24.41 0.5 eq 3 Isobutanol, 124.4 73 175 1514.97 0.75 eq 4 Isobutanol, 30.8 96 55 10 8.11 28 2 eq 52-Ethyl-1-hexanol, 162.1 64 430 30 26.19 0.5 eq 6 2-Ethyl-1-hexanol,57.3 90 120 15 13.83 25 1.0 eq 7 Isoamyl alcohol, 76.8 85 10.86 35 1.0eq 8 Isoamyl alcohol, 184.0 58 23.11 0.5 eq 9 Isoamyl alcohol, 43.6 9310 7.90 1.2 eq 10 2-Ethyl-1-hexanol, 21.7 98 1.2 eq *⁾estimated esterconversion, 1-[(AV(product)-15(MSA))/AV(MA9-DAMe)], slight error due tochange in Mw; **⁾Viscosity Standard S200 @100° C. KV = 22.13 cSt, ρ =0.7914 g/mL, η = 17.51 cP, test value KV = 24.88 cSt).

The full esters have a lower viscosity than the half ester of the samealcohol. The starting material (i.e., 9-DAMe) has a golden-red color.During the esterification the red disappears. The full esters are veryclear golden oils. The half esters show a color between the startingmaterial and the full esters. The redness decreases with the estercontent of the oils. Pour points are determined for some of the higherconverted esters, which shows a lower viscosity at room temperature.Values between −25 and −35° C. are found. Free carboxylic groupsincrease the viscosity of the oils. The hydrolyzed product of MA9-DAMe,the diacid, has a high viscosity at room temperature.

Dispersants

The dispersant composition may be derived from a nitrogen-containingreagent and/or an oxygen-containing reagent, a functionalized monomerand/or polymer, and an enophilic reagent, wherein the enophilic reagentcomprises an enophilic acid, anhydride and/or ester reagent (e.g.,maleic anhydride). In an embodiment, the enophilic acid, anhydrideand/or ester reagent may be reacted with the functionalized monomerand/or polymer to form an enophilic reagent modified functionalizedmonomer or polymer, which may then be reacted with thenitrogen-containing reagent and/or oxygen containing reagent to form thedispersant. In an embodiment, the enophilic acid, anhydride and/or esterreagent may be reacted with the nitrogen-containing reagent and/oroxygen containing reagent to form an enophilic reagent modifiednitrogen-containing reagent and/or oxygen-containing reagent, which maythen be reacted with the functionalized monomer and/or polymer to formthe dispersant. The functionalized monomer or polymer, or enophilicreagent modified functionalized monomer or polymer, optionally incombination with an alkenylsuccinic acid and/or anhydride (e.g.,polyisobutenylsuccinic anhydride), may be reacted with thenitrogen-containing reagent and/or an oxygen-containing reagent to formthe dispersant. The dispersant may be used in a lubricant, functionalfluid or fuel composition.

The dispersant may comprise the reaction product of anitrogen-containing reagent or an oxygen-containing reagent, with: (i)the reaction product of an enophilic acid reagent with a functionalizedmonomer comprising a hydrocarbyl group with one or more carbon-carbondouble bonds and one or more functional groups attached to thehydrocarbyl group, the hydrocarbyl group containing at least about 5carbon atoms, or from about 5 to about 30 carbon atoms, or from about 6to about 30 carbon atoms, or from about 8 to about 30 carbon atoms, orfrom about 10 to about 30 carbon atoms, or from about 12 to about 30carbon atoms, or from about 14 to about 30 carbon atoms, or from about16 to about 30 carbon atoms, or from about 5 to about 18 carbon atoms,or from about 5 to about 18 carbon atoms, or about 18 carbon atoms, orfrom about 8 to about 12 carbon atoms, or about 10 carbon atoms, thefunctional group comprising a carboxylic acid or anhydride; (ii) apolymer (or oligomer) derived from one or more of the functionalizedmonomers (i); (iii) a copolymer (or co-oligomer) derived from one ormore of the functionalized monomers (i) and one or more olefincomonomers; (iv) the reaction product of an enophilic acid, anhydrideand/or ester reagent with the polymer (ii) or copolymer (iii); or (v) amixture of two or more of (i), (ii), (iii) and (iv). The reactionproduct (iv) may comprise a polyfunctionalized monomer or polymer. Theolefin comonomer may contain from 2 to about 30 carbon atoms, or fromabout 6 to about 24 carbon atoms.

The enophilic acid, anhydride or ester reagent may comprise any of thosediscussed above, including maleic anhydride. The nitrogen-containingreagents and oxygen containing reagents may be any of those discussedabove. The dispersant may comprise one or more amides, diamides,triamides, imides, esters, di-esters, tri-esters, amide esters, aminesalts, ammonium salts, mixtures of two or more thereof, and the like.These may be prepared using the procedures described above.

The functionalized or polyfunctionalized polymer may comprise ahomopolymer (or homo-oligomer) derived from the functionalized monomer,or a copolymer (or co-oligomer) derived from one or more of thefunctionalized monomers and/or one or more olefin comonomers. Thepolymer may contain at least about 30 mole percent of repeating unitsderived from one or more of the functionalized monomers, or at leastabout 50 mole percent, or at least about 70 mole percent, or from about30 to about 100 mole percent, or from about 50 to about 100 percent, orfrom about 70 to about 100 mole percent. The olefin comonomer maycontain from 2 to about 30 carbon atoms, or from about 6 to about 24carbon atoms. The polymer may have any desired molecular weightdepending on its end use, for example, a number average molecular weightin the range from about 100 to about 10,000, or from about 300 to about10,000, or from about 500 to about 1000, or from about 700 to about50,000, or from about 1000 to about 5000, or from about 1000 to about3000, as determined by GPC. The polymer may be prepared using theprocedures described above. The polymer may be partially or fullyhydrogenated.

The functionalized monomer (i), polymer (ii), copolymer (iii) and/orreaction product (iv) may optionally be mixed with an alkenylsuccinicacid or anhydride, such as polyisobutenylsuccinic anhydride, and thenreacted with the nitrogen-containing reagent and/or oxygen-containingreagent. The alkenylsuccinic anhydride may have a number averagemolecular weight in the range from about 750 to about 3000. The ratio ofequivalents of the functionalized monomer (i), polymer (ii), copolymer(iii), and/or reaction product (iv) to equivalents of thealkenylsuccinic acid or anhydride (e.g., polyisobutenylsuccinicanhydride) may be in the range from about 1 to about 4, or from about 1to about 2. The weight of an equivalent of the monomer (i), polymer(ii), copolymer (iii) or reaction product (iv) as well as thealkenylsuccinic acid or anhydride is dependent on the number of carbonylgroups to be reacted with the amine or an alcohol reagent. For example,if one mole of a functionalized monomer (i) has two carbonyl groups inits molecular structure and one of the carbonyl groups is reacted withan amine to form a cyclic imide, the functionalized monomer (i) wouldhave an equivalent weight equal to its molecular weight. Conversely, ifboth carbonyl groups were to be reacted with the amine to form a diamideor a monohydric alcohol to form a diester, the equivalent weight of thefunctionalized monomer (i) would be one-half of its molecular weight.

Alternatively, the alkenyl succinic acid and/or anhydride may beseparately reacted with the nitrogen-containing reagent to form asuccinimide (e.g., polyisobutenyl succinimide) and/or an oxygencontaining reagent to form a succinic acid ester, and then mixed withthe above-indicated dispersant. The alkenylsuccinic acid and/oranhydride may have a number average molecular weight in the range fromabout 750 to about 3000.

The dispersants may be post-treated or post-reacted by conventionalmethods using any of a variety of agents. Among these may be boroncompounds (such as boric acid), urea, thiourea, dimercaptothiadiazoles,carbon disulfide, aldehydes, ketones, carboxylic acids such asterephthalic acid, hydrocarbon-substituted succinic anhydrides, maleicanhydride, nitriles, epoxides, phosphorus compounds, and the like.

Detergents

The detergent composition may comprise a neutral or overbased detergentderived from a metal or metal compound, and one or more of theabove-discussed functionalized monomers and/or polymers, and anenophilic reagent, wherein the enophilic reagent comprises an enophilicacid, anhydride and/or ester reagent (e.g., maleic anhydride). In anembodiment, the enophilic acid, anhydride and/or ester reagent may bereacted with the functionalized monomer and/or polymer to form anenophilic reagent modified functionalized monomer and/or polymer, whichmay then be reacted with the metal or metal compound to form thedetergent. In an embodiment, the enophilic reagent may be reacted withthe metal or metal compound to form an enophilic reagent modified metalor metal compound, which may then be reacted with the functionalizedmonomer and/or polymer to form the detergent. The functionalized polymermay be derived from the functionalized monomer and a comonomer. Thecomonomer may comprise an olefin containing from 2 to about 30 carbonatoms, or from about 6 to about 24 carbon atoms.

The detergent may comprise a neutral or overbased material derived froma metal or metal compound, and: (i) the reaction product of an enophilicacid reagent with a functionalized monomer comprising a hydrocarbylgroup with one or more carbon-carbon double bonds and one or morefunctional groups attached to the hydrocarbyl group, the hydrocarbylgroup containing at least about 5 carbon atoms, or from about 5 to about30 carbon atoms, or from about 6 to about 30 carbon atoms, or from about8 to about 30 carbon atoms, or from about 10 to about 30 carbon atoms,or from about 12 to about 30 carbon atoms, or from about 14 to about 30carbon atoms, or from about 16 to about 30 carbon atoms, or from about 5to about 18 carbon atoms, or from about 12 to about 18 carbon atoms, orabout 18 carbon atoms, or from about 8 to about 12 carbon atoms, orabout 10 carbon atoms, the functional group comprising a carboxylic acidgroup or an anhydride thereof; (ii) a polymer (or oligomer) derived fromone or more of the functionalized monomers (i); (iii) a copolymer (orco-oligomer) derived from one or more of the functionalized monomers (i)and one or more olefin comonomers; (iv) the reaction product of anenophilic acid, anhydride or ester reagent with the polymer (ii) and/orcopolymer (iii) to form a polyfunctionalized polymer or copolymer; or(v) a mixture of two or more of (i), (ii), (iii) and (iv). The olefincomonomer may contain from 2 to about 30 carbon atoms, or from about 6to about 24 carbon atoms. The functionalized or polyfunctionalizedpolymer (or oligomer, copolymer or co-oligomer) may contain at leastabout 30 mole percent of repeating units derived from the functionalizedor polyfunctionalized monomer, or at least about 50 mole percent, or atleast about 70 mole percent, or from about 30 to about 100 mole percent,or from about 50 to about 100 percent, or from about 70 to about 100mole percent. The enophilic acid, anhydride or ester reagent maycomprise any of those discussed above, including maleic anhydride. Themonomer (i), polymer (ii), copolymer (iii) and/or reaction product (iv),may be mixed with an alkarylsulfonic acid (e.g., alkylbenzenesulfonicacid) prior to or during the reaction to form the overbased material.The functionalized or polyfunctionalized monomer or polymer may have anydesired molecular weight, for example, a number average molecular weightin the range from about 100 to about 50,000 or higher, or from about 300to about 50,000, or from about 150 to about 20,000, or from about 200 toabout 10,000, or from about 300 to about 5000, as determined by gelpermeation chromatography (GPC), NMR spectroscopy, vapor phase osometry(VPO), wet analytical techniques such as acid number, base number,saponification number of oxirane number, and the like. The monomer orpolymer may be prepared using the procedures described above.

The term “overbased” is a term of art which is generic to well knownclasses of metal salts or complexes. These products or materials havealso been referred to as “basic”, “superbased”, “hyperbased”,“complexes”, “metal complexes”, “high-metal containing salts”, and thelike. Overbased products or materials may be regarded as metal salts orcomplexes characterized by a metal content in excess of that which wouldbe present according to the stoichiometry of the metal and theparticular acidic organic compound, e.g., a carboxylic acid, reactedwith the metal. Thus, if a monocarboxylic acid,

RCOOH

is neutralized with a basic metal compound, e.g., calcium hydroxide, the“neutral” or “normal” metal salt produced will contain one equivalent ofcalcium for each equivalent of acid, i.e.,

R—C(═O)—O—Ca—O—C(═O)—R

However, various processes may be used to produce an inert organicliquid solution of a product containing more than the stoichiometricamount of metal. This solution may be referred to as overbased productor material. Following these procedures, the carboxylic acid may bereacted with a metal base. The resulting product may contain an amountof metal in excess of that necessary to neutralize the acid. Forexample, 4 times as much metal as present in the neutral salt, or ametal excess of 3 equivalents, may be used. The actual stoichiometricexcess of metal may vary considerably, for example, from about 0.1equivalent to about 40 or more equivalents depending on the reactions,the process conditions, and the like. An equivalent of a metal isdependent upon its valence, and the nature/structure of the functionalgroup in the substrate. Thus, for a reaction with a substrate, such as amonocarboxylic acid, one mole of a monovalent metal such as sodiumprovides one equivalent of the metal, whereas 0.5 moles of a divalentmetal such as calcium are required to provide one equivalent of suchmetal. The number of equivalents of a metal base in a detergent can bemeasured using standard techniques (e.g., titration using bromophenolblue as the indicator to measure total base number, TBN).

The term “metal ratio” is used herein to designate the ratio of thetotal chemical equivalents of the metal in the overbased material (e.g.,a metal carboxylate) to the chemical equivalents of the metal in theproduct which would be expected to result from the reaction between theorganic material to be overbased (e.g., carboxylic acid) and themetal-containing reactant (e.g., calcium hydroxide, barium oxide, etc.)according to the known chemical reactivity and stoichiometry of the tworeactants. Thus, in the normal or neutral calcium carboxylate discussedabove, the metal ratio is one, and in the overbased carboxylate, themetal ratio is 4, or more. If there is present in the material to beoverbased more than one compound capable of reacting with the metal, the“metal ratio” of the product will depend upon whether the number ofequivalents of metal in the overbased product is compared to the numberof equivalents expected to be present for a given single component or acombination of all such components.

The neutral or overbased product or material useful as a detergent maybe neutral or may be overbased with a metal ratio in excess of 1 andgenerally up to about 40 or more. The metal ratio may be in the rangefrom an excess of 1 up to about 35, or from an excess of 1 up to about30. The metal ratio may range from about 1.1 or about 1.5 to about 40;or from about 1.1 or about 1.5 to about 35; or from about 1.1 or about1.5 to about 30; or from about 1.1 or about 1.5 to about 25. The metalratio may range from about 1.5 to about 30 or 40, or from about 5 toabout 30 or 40, or from about 10 to about 30 or 40, or from about 15 toabout 30 or 40. The metal ratio may range from about 20 to about 30.

The overbased product or material may be prepared using thefunctionalized monomer (i), polymer (ii), copolymer (iii) and/orreaction product (iv) of the invention, alone or in combination with analkarylsulfonic acid. The monomer (i), polymer (ii), copolymer (iii),and/or reaction product (iv) and, optionally, the alkarylsulfonic acid,may be referred to herein as (1) the organic material to be overbased.The overbased product or material may be prepared by the reaction of amixture of (1) the organic material to be overbased, (2) a reactionmedium comprising an inert, organic solvent/diluent for the organicmaterial to be overbased, a stoichiometric excess of (3) at least onemetal base, and (4) a promoter, with (5) an acidic material. Theoverbased product or material may be borated by reacting the overbasedproduct or material with a boron containing compound.

The alkarylsulfonic acids may include alkylbenzenesulfonic acids whereinthe alkyl group contains at least about 8 carbon atoms, or from about 8to about 30 carbon atoms. The ratio of equivalents of the functionalizedmonomer (i), polymer (ii), copolymer (iii) and/or reaction product (iv)to the alkarylsulfonic acid may be from about 1 to about 5, or fromabout 1 to about 2. The weight of an equivalent of an alkarylsulfonicacid agent is dependent on the number of sulfonic acid groups in thealkarylsulfonic acid that are reactive with the metal base (3). Forexample, one mole of an alkarylsulfonic acid having one sulfonic acidavailable for reaction with the metal base would have an equivalentweight equal to the molecular weight of the alkarylsulfonic acid.

The organic material to be overbased (1) may be soluble in the reactionmedium (2). When the reaction medium (2) is a petroleum fraction (e.g.,mineral oil), the organic material to be overbased may be oil-soluble.However, if another reaction medium is employed (e.g., aromatichydrocarbons, aliphatic hydrocarbons, kerosene, etc.) the organicmaterial to be overbased (1) may not necessarily be soluble in mineraloil as long as it is soluble in the given reaction medium. Whenreferring to the solubility of the (1) organic material to be overbasedin (2) the reaction medium, it is to be understood that the organicmaterial to be overbased may be soluble in the reaction medium to theextent of at least one gram of the material to be overbased per liter ofreaction medium at 20° C.

The reaction medium (2) may be a substantially inert, organicsolvent/diluent for the (1) organic material to be overbased. Examplesof the reaction medium (2) may include alkanes and haloalkanes of about5 to about 18 carbons, polyhalo- and perhalo-alkanes of up to about 6carbons, cycloalkanes of about 5 or more carbons, the correspondingalkyl- and/or halo-substituted cycloalkanes, aryl hydrocarbons,alkylaryl hydrocarbons, haloaryl hydrocarbons, ethers such as dialkylethers, alkyl aryl ethers, cycloalkyl ethers, cycloalkylalkyl ethers,alkanols, alkylene glycols, polyalkylene glycols, alkyl ethers ofalkylene glycols and polyalkylene glycols, dibasic alkanoic aciddiesters, silicate esters, and mixtures of these. Examples may includepetroleum ether, Stoddard Solvent, pentane, hexane, octane, isooctane,undecane, tetradecane, cyclopentane, cyclohexane, isopropylcyclohexane,1,4-dimethylcyclohexane, cyclooctane, benzene, toluene, xylene, ethylbenzene, tert-butyl-benzene, halobenzenes such as mono- andpolychlorobenzenes including chlorobenzene per se and3,4-dichlorotoluene, mineral oils, n-propylether, isopropylether,isobutylether, n-amylether, methyl-n-amylether, cyclohexylether,ethoxycyclohexane, methoxybenzene, isopropoxybenzene, p-methoxytoluene,methanol, ethanol, propanol, isopropanol, hexanol, n-octyl alcohol,n-decyl alcohol, alkylene glycols such as ethylene glycol and propyleneglycol, diethyl ketone, dipropyl ketone, methylbutyl ketone,acetophenone, 1,2-difluorotetrachloroethane, dichlorofluoromethane,1,2-dibromotetrafluoroethane, trichlorofluoromethane, 1-chloropentane,1,3-dichlorohexane, formamide, dimethylformamide, acetamide,dimethylacetamide, diethylacetamide, propionamide, diisooctyl azelate,polyethylene glycols, polypropylene glycols, hexa-2-ethylbutoxydisiloxane, etc.

Also useful as the reaction medium (2) may be low molecular weightliquid polymers, generally classified as oligomers, which may includedimers, trimers, tetramers, pentamers, etc. Illustrative of this classof materials may be such liquids as propylene tetramers, isobutylenedimers, and the like.

The metal base (3) used in preparing the neutral or overbased productsor materials may comprise one or more alkali metals, alkaline-earthmetals, titanium, zirconium, molybdenum, iron, copper, zinc, aluminum,mixture of two or more thereof, or basically reacting compounds thereof.Lithium, sodium, potassium, magnesium, calcium, strontium, barium, zinc,or a mixture of two or more thereof, may be useful.

The basically reacting compound may comprise any compound of any of theforegoing metals or mixtures of metals that is more basic than thecorresponding metal salt of the acidic material (5) used in preparingthe overbased product or material. These compounds may includehydroxides, alkoxides, nitrites, carboxylates, phosphites, sulfites,hydrogen sulfites, carbonates, hydrogen carbonates, borates, hydroxides,oxides, alkoxides, amides, etc. The nitrites, carboxylates, phosphites,alkoxides, carbonates, borates, hydroxides and oxides may be useful. Thehydroxides, oxides, alkoxides and carbonates may be useful.

The promoters (4), that is, the materials which facilitate theincorporation of an excess metal into the overbased product may includethose materials that are less acidic than the acidic material (5) usedin making the overbased products. These may include alcoholic andphenolic promoters. The alcohol promoters may include alkanols of one toabout 12 carbon atoms. Phenolic promoters may include a variety ofhydroxy-substituted benzenes and naphthalenes. The phenolic promotersmay include alkylated phenols such as heptylphenol, octylphenol,nonylphenol, dodecyl phenol, propylene tetramer phenol, and mixtures oftwo or more thereof.

The promoters (4) may include water, ammonium hydroxide, nitromethane,organic acids, of up to about 8 carbon atoms, metal complexing agentssuch as the salicylaldoximes (e.g., alkyl(C₁-C₂₀)salicylaldoxime), andalkali metal hydroxides such as lithium hydroxide, sodium hydroxide andpotassium hydroxide, and mono- and polyhydric alcohols of up to about 30carbon atoms, or up to about 20 carbon atoms, or up to about 10 carbonatoms. Examples may include methanol, ethanol, isopropanol, amylalcohol, cyclohexanol, octanol, dodecanol, decanol, behenyl alcohol,ethylene glycol, diethylene glycol, triethylene glycol, monomethyletherof ethylene glycol, trimethylene glycol, hexamethylene glycol, glycerol,pentaerythritol, benzyl alcohol, phenylethyl alcohol, sorbitol,nitropropanol, chloroethanol, aminoethanol, cinnamyl alcohol, allylalcohol, and the like.

The acidic material (5) may comprise one or more of carbamic acid,acetic acid, formic acid, boric acid, trinitromethane, SO₂, CO₂, sourcesof said acids, and mixtures thereof. CO₂ and SO₂, and sources thereof,are preferred. Sources of CO₂ may include ammonium carbonate andethylene carbonate. Sources of SO₂ may include sulfurous acid,thiosulfuric acid, dithionous acid, and/or their salts.

The overbased products or materials may be prepared by reacting amixture of the organic material to be overbased, the reaction medium,the metal base, and the promoter, with the acidic material. A chemicalreaction may then ensue. The temperature at which the acidic materialreacts with the remainder of the reaction mass may depend upon thepromoter that is used. With a phenolic promoter, the temperature mayrange from about 60° C. to about 300° C., or from about 100° C. to about200° C. When an alcohol or mercaptan is used as the promoter, thetemperature may not exceed the reflux temperature of the reactionmixture. The exact nature of the resulting overbased product or materialmay not be known. However, it may be described for purposes of thepresent specification as a single phase homogeneous mixture of thereaction medium and either a metal complex formed from the metal base,the acidic material, and the organic material to be overbased and/or anamorphous metal salt formed from the reaction of the acidic materialwith the metal base and the organic material to be overbased.

The overbased product or material may comprise a boron-containingoverbased product or material. These borated overbased products ormaterials may be prepared by reacting at least one overbased productwith at least one boron compound. The boron compound may comprise one ormore of boron oxide, boron oxide hydrate, boron trioxide, borontrifluoride, boron tribromide, boron trichloride, boron acids such asboronic acid (i.e., alkyl-B(OH)₂ or aryl-B(OH)₂), boric acid (i.e.,H₃BO₃), tetraboric acid (i.e., H₂B₄O₇), metaboric acid (i.e., HBO₂),boron anhydrides, and various esters of such boron acids. The boronicacids may include methyl boronic acid, phenyl-boronic acid, cyclohexylboronic acid, p-heptylphenyl boronic acid, dodecyl boronic acid, or amixture of two or more thereof. The boron acid esters may include mono-,di-, and or tri-organic esters of boric acid with alcohols or phenolssuch as, e.g., methanol, ethanol, isopropanol, cyclohexanol,cyclopentanol, 1-octanol, 2-octanol, dodecanol, behenyl alcohol, oleylalcohol, stearyl alcohol, benzyl alcohol, 2-butyl cyclohexanol, ethyleneglycol, propylene glycol, trimethylene glycol, 1,3-butanediol;2,4-hexanediol, 1,2-cyclohexanediol, 1,3-octanediol, glycerol,pentaerythritol diethylene glycol, or a mixture of two or more thereof.

The reaction of the overbased product with the boron compound can beeffected using standard mixing techniques. The ratio of equivalents ofthe boron compound to equivalents of the overbased product may range upto about 40:1 or higher, or in the range of about 0.05:1 to about 30:1,or in the range of about 0.2:1 to about 20:1. Equivalent ratios of about0.5:1 to about 5:1, or about 0.5:1 to about 2:1, or about 1:1 may beused. An equivalent of a boron compound may be based upon the number ofmoles of boron in the compound. Thus, boric acid has an equivalentweight equal to its molecular weight, while tetraboric acid has anequivalent weight equal to one-fourth of its molecular weight. Anequivalent weight of an overbased product or material is based upon thenumber of equivalents of metal in the overbased product available toreact with the boron. Thus, an overbased product having one equivalentof metal available to react with the boron has an equivalent weightequal to its actual weight. An overbased product having two equivalentsof metal available to react with the boron has an equivalent weightequal to one-half its actual weight. The temperature can range fromabout room temperature up to the decomposition temperature of thereactants, or desired products having the lowest such temperature, andmay be in the range of about 20° C. to about 200° C., or about 20° C. toabout 150° C., or about 50° C. to about 150° C., or about 80° C. toabout 120° C. The reaction time may be the time required to form thedesired concentration of metal borate (e.g., sodium borate) in theboron-containing overbased product. The reaction time may be from about0.5 to about 50 hours, or from about 1 to about 25 hours, or about 1 toabout 15 hours, or about 4 to about 12 hours.

The Lubricant and Functional Fluid Compositions

The lubricant and/or functional fluid compositions of the invention maycomprise one or more base oils comprising one or more of theabove-identified functionalized or polyfunctionalized monomers orpolymers. These base oils may be referred to as functional base oils.These base oils may be blended with one or more conventional base oils.The dispersants and/or detergents described above, which may be derivedfrom one or more of the above-identified functionalized orpolyfunctional monomers or polymers, may be used in these lubricantsand/or functional fluids.

The lubricant compositions may be effective as engine oil or crankcaselubricating oils for spark-ignited and compression-ignited internalcombustion engines, including automobile and truck engines, two-strokecycle engines, aviation piston engines, marine and diesel engines,stationary gas engines, and the like. The functional fluids may comprisea driveline fluid such as an automatic transmission fluid, manualtransmission fluid, transaxle lubricant, fluid for continuously variabletransmissions, dual clutch automatic transmission fluid, farm tractorfluid, fluids for hybrid vehicle transmission, or gear oil. Thefunctional fluid may comprise a metal-working lubricant, hydraulicfluid, or other lubricating oil or grease composition.

In an embodiment, the base oil may comprise one or more of theabove-identified functionalized or polyfunctionalized monomers orpolymers. When the above-identified functionalized or polyfunctionalizedpolymer is a copolymer, the copolymer may be derived from one or more ofthe above-discussed functionalized or polyfunctionalized monomers andone or more olefin comonomers. The copolymer may contain from about 5 toabout 30 mole percent, or from about 10 to about 25 mole percent,repeating units derived from the functionalized or polyfunctionalizedmonomer. The polymer may be partially or fully hydrogenated. The polymermay have a number average molecular weight in the range from about 100to about 50,000, or from about 300 to about 20,000, or from about 200 toabout 10,000, or from about 300 to about 5000, or from about 500 toabout 3000.

The base oil may comprise a functionalized polymer in the form of afunctionalized copolymer (or co-oligomer) containing structuralrepeating units derived from a functionalized or polyfunctionalizedmonomer and structural repeating units derived from an alpha olefin.This base oil may be referred to as a functional base oil. This base oilmay be referred to as a functionalized polyalphaolefin. This base oilmay be used in lubricants or functional fuels employed as engine oilsand/or drive line fuels. The functionalized or polyfunctionalizedmonomers may comprise esters of unsaturated carboxylic acids of about 4to about 30 carbon atoms, or from about 5 to about 18 carbon atoms. Theunsaturated carboxylic acids may be fatty acids. The fatty acids maycomprise 9-decenoic acid (9DA), 10-undecenoic acid (10UDA), 9-dodecenoicacid (9DDA), 9-octadecenoic acid (9ODDA), mixtures of two or morethereof, and the like. The esters may comprise methyl-, di-methyl,ethyl-, n-propyl-, isopropyl-, n-butyl-, sec-butyl-, tert-butyl- and/orpentaerythritol esters of 9DA, 10UDA, 9DDA, 9ODDA, mixtures of two ormore thereof, and the like. Examples of the 9DA esters, 10UDA esters,9DDA esters, and 9ODDA esters may include methyl 9-decenoate (“9-DAME”),methyl 10-undecenoate (“10-UDAME”), methyl 9-dodecenoate (“9-DDAME”) andmethyl 9-octadecenoate (“9-ODDAME”), respectively. The alpha olefin mayhave from 2 to about 30 carbon atoms, or from 2 to about 24 carbonatoms, or from about 4 to about 24 carbon atoms, or from about 6 toabout 24 carbon atoms. The alpha olefin may be linear or branched. Thealpha olefin may comprise one or more of ethene, 1-propene, 1-butene,1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene,1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene,1-hexadecene, 1-octadecene, 1-eicosene, or a mixture of two or morethereof. The molar ratio of functionalized or polyfunctionalized monomerto the alpha olefin may range from about 100:1 to about 1:100, or fromabout 50:1 to about 1:50, or from about 10:1 to about, 1:10, or from 5:1to about 1:5, or from about 2:1 to about 1:2, or from about 1.5:1 toabout 1:1.5, or about 1:1. The functional base oil may comprise acopolymer (or co-oligomer) comprising structural units derived frommethyl 9-decenoate and 1-decene. The molar ratio of methyl 9-decenoateto 1-decene may be in the range from about 10:1 to about 1:1.

The base oil may comprise a polyester derived from a malienated fattyester and one or more alcohols and/or aminoalcohols. This base oil maybe referred to as a functional base oil. This base oil may be used inthe fill-for-life lubricants or functional fluids. The maleinated fattyester may be derived from an ester of an unsaturated carboxylic acid andmaleic anhydride. The unsaturated carboxylic acid may have from about 4to about 30 carbon atoms, or from about 5 to about 18 carbon atoms. Theunsaturated carboxylic acids may be fatty acids. The fatty acids maycomprise 9-decenoic acid (9DA), 10-undecenoic acid (10UDA), 9-dodecenoicacid (9DDA), 9-octadecenoic acid (9ODDA), mixtures of two or morethereof, and the like. The esters may comprise methyl-, ethyl-,n-propyl-, isopropyl-, n-butyl-, sec-butyl-, tert-butyl- and/orpentaerythritol esters of 9DA, 10UDA, 9DDA, 9ODDA, mixtures of two ormore thereof, and the like. Examples of the 9DA esters, 10UDA esters,9DDA esters, and 9ODDA esters may include methyl 9-decenoate (“9-DAME”),methyl 10-undecenoate (“10-UDAME”), methyl 9-dodecenoate (“9-DDAME”) andmethyl 9-octadecenoate (“9-ODDAME”), respectively. The alcohols maycomprise one or more of the alcohols or amino-alcohols discussed above.These may include isobutyl alcohol, iso-amyl alcohol, 2-ethylhexylalcohol, neopentyl alcohol, mixtures of two or more thereof, and thelike. The polyester functional base oil may comprise a monohydric orpolyhydric alcohol ester of maleinated methyl 9-decenoate. Thesepolyester base oils may be biodegradable and may be used as highperformance lubricant base oils.

The functional base oil may comprise a mixture of one or more of theabove-identified functionalized copolymer base oils, and one or more ofthe above-identified polyester based oils. The weight ratio offunctionalized copolymer base oil to polyester base oil may be in therange from about 10:1 to about 1:10, or from about 5:1 to about 1:5, orfrom about 2:1 to about 1:2, or about 1:1.

The functional base oil may have any desired molecular weight, forexample, a number average molecular weight in the range from 100 toabout 20,000, or from about 250 to about 20,000, or from about 500 toabout 20,000, or from about 700 to about 10,000, or from about 1000 toabout 5000, or from about 1000 to about 3000, as determined by GPC.

The functional base oil may have a kinetic viscosity (ASTM D-445) in therange from about 2 to about 1000 cSt at 100° C., or from about 2 toabout 500, or from about 2 to about 100, or from about 4 to about 10cSt. The base oil may have a viscosity up to about 35 cSt at 100° C., orin the range from about 3 to about 35 cSt, or in the range from about 5to about 35 cSt at 100° C.

The functional base oil may have a viscosity index (ASTM D2270) in therange from about 120 to about 250, or from about 130 to about 150.

The functional base oil may have a pour point (ASTM D97) in the rangefrom about −20 to about −70° C., or from about −30 to about −45° C., orabout −40° C.

The functional base oil may have an aniline point (ASTM D611) in therange from about 25 to about 120° C., or from about 50 to about 100° C.

The functional base oil may have oxidation induction time (ASTM D6186)at 210° C. in the range from about 1 to about 10 minutes, or from about1 to about 3 minutes, or from about 5 to about 10 minutes.

The functional base oil may have an oxidation onset temperature (ASTME2009) in the range from about 170° C. to about 220° C., or from about190° C. to about 210C.

The cold crank simulator viscosity test values (ASTM D5293) for thefunctional base oil may be in the range from about 13000 to about 9500cP, or from about 7000 to about 9500 cP, at a temperature of −15° C.; orin the range from about 7000 to about 6600 cP, or from about 1000 toabout 6200 cP, at a temperature of −35° C.

The evaporation loss (ASTM D5293) for the functional base oils may be inthe range from about 5 to about 15%, or from about 4 to about 7%.

The functional base oils may exhibit enhanced values for hightemperature shear stability, fuel economy, deposit control, oxidativestability, thermal stability, and the like.

The functional base oil may be used alone as the base oil or may beblended with an American Petroleum Institute (API) Group II, III, IV orV base oil, a natural oil, an estolide fluid, or a mixture of two ormore thereof. Examples of the natural oil may include soybean oil,rapeseed oil, and the like. The blended base oil may contain from about1% to about 75%, or from about 5% to about 60% by weight of thefunctionalized copolymer and/or polyester.

The API Group I-V base oils have the following characteristics:

Sulfur Base Oil Category (%) Saturates (%) Viscosity Index Group I >0.03and/or <90 80 to 120 Group II ≦0.03 and ≧90 80 to 120 Group III ≦0.03and ≧90 ≧120 Group IV All polyalphaolefins (PAO) Group V All others notincluded in Groups I, II, III, or IVThe Group I-III base oils are mineral oils.

The base oil may be present in the lubricant or functional fluidcomposition at a concentration of greater than about 60% by weight basedon the overall weight of the lubricant or functional fluid composition,or greater than about 65% by weight, or greater than about 70% byweight, or greater than about 75% by weight.

The lubricant or functional fluid may further comprise one or more ofthe above-identified dispersants and/or detergents. The dispersant maybe present in the lubricant or functional fluid composition at aconcentration in the range from about 0.01 to about 20% by weight, orfrom about 0.1 to about 15% by weight based on the weight of thelubricant or functional fluid. The detergent may be present in thelubricant or functional fluid composition at a concentration in therange from about 0.01% by weight to about 50% by weight, or from about1% by weight to about 30% by weight based on the weight of the lubricantor functional fluid composition. The detergent may be present in anamount suitable to provide a TBN (total base number) in the range fromabout 2 to about 100 to the lubricant composition, or from about 3 toabout 50. TBN is the amount of acid (perchloric or hydrochloric) neededto neutralize all or part of a material's basicity, expressed asmilligrams of KOH per gram of sample.

The lubricant or functional fluid composition may further comprise oneor more additional functional additives, including, for example, one ormore supplemental detergents and/or dispersants, as well as corrosion-and oxidation-inhibiting agents, pour point depressing agents, extremepressure (EP) agents, antiwear agents, viscosity index (VI) improvers,friction modifiers (e.g., fatty friction modifiers), hindered amine,phenolic and/or sulfurized inhibitors, antioxidants, metal cuttingadditives (e.g., sulfur chloride), antimicrobial additives, colorstabilizers, viscosity modifiers (e.g., ethylene propylene diene (EPDM)viscosity modifiers), demulsifiers, seal swelling agents, anti-foamagents, mixtures of two or more thereof, and the like.

The supplemental detergent may include one or more overbased materialsprepared by reacting an acidic material (typically an inorganic acid orlower carboxylic acid, such as carbon dioxide) with a mixture comprisingan acidic organic compound, a reaction medium comprising at least oneinert, organic solvent (mineral oil, naphtha, toluene, xylene, etc.) forsaid acidic organic material, a stoichiometric excess of a metal base,and a promoter such as a calcium chloride, acetic acid, phenol oralcohol. The acidic organic material may have a sufficient number ofcarbon atoms to provide a degree of solubility in oil. The metal may bezinc, sodium, calcium, barium, magnesium, or a mixture of two or morethereof. The metal ratio may be from an excess of 1 to about 40, or inthe range from about 1.1 to about 40. These detergents may includeoverbased sulfonates, overbased phenates, mixtures thereof, and thelike.

The supplemental dispersants that may be used may include any dispersantknown in the art which may be suitable for the lubricant or functionalfluid compositions of this invention. These may include:

(1) Reaction products of carboxylic acids (or derivatives thereof), withnitrogen containing compounds such as amines, hydroxy amines, organichydroxy compounds such as phenols and alcohols, and/or basic inorganicmaterials. These may be referred to as carboxylic dispersants. These mayinclude succinimide dispersants, such as polyisobutenylsuccinimide.

(2) Reaction products of relatively high molecular weight aliphatic oralicyclic halides with amines, for example, polyalkylene polyamines.These may be referred to as “amine dispersants.”

(3) Reaction products of alkylphenols with aldehydes (e.g.,formaldehyde) and amines (e.g., polyalkylene polyamines), which may bereferred to as “Mannich dispersants.”

(4) Products obtained by post-treating the carboxylic, amine or Mannichdispersants with such reagents as urea, thiourea, carbon disulfide,aldehydes, ketones, carboxylic acids, hydrocarbon-substituted succinicanhydrides, nitriles, epoxides, boron compounds, phosphorus compounds orthe like.

(5) Interpolymers of oil-solubilizing monomers such as decylmethacrylate, vinyl decyl ether and high molecular weight olefins withmonomers containing polar substituents, e.g., aminoalkyl acrylates oracrylamides and poly-(oxyethylene)-substituted acrylates. These may bereferred to as “polymeric dispersants.”

Extreme pressure (EP) agents and corrosion and oxidation-inhibitingagents which may be included in the lubricants and/or functional fluidsof the invention, may include chlorinated aliphatic hydrocarbons such aschlorinated wax; organic sulfides and polysulfides such as benzyldisulfide, bis(chlorobenzyl)disulfide, dibutyl tetrasulfide, sulfurizedmethyl ester of oleic acid, sulfurized alkylphenol, sulfurizeddipentene, and sulfurized terpene; phosphosulfurized hydrocarbons suchas the reaction product of a phosphorus sulfide with turpentine ormethyl oleate, phosphorus esters including principally dihydrocarbyl andtrihydrocarbyl phosphites such as dibutyl phosphite, diheptyl phosphite,dicyclohexyl phosphite, pentylphenyl phosphite, dipentylphenylphosphite, tridecyl phosphite, distearyl phosphite, dimethyl naphthylphosphite, oleyl 4-pentylphenyl phosphite, polypropylene (molecularweight 500)-substituted phenyl phosphite, diisobutyl-substituted phenylphosphite; metal thiocarbamates, such as zinc dioctyldithiocarbamate,and barium heptylphenyl dithiocarbamate; Group II metalphosphorodithioates such as zinc dicyclohexylphosphorodithioate, zincdioctyl phosphorodithioate, barium di(heptylphenyl)phosphorodithioate,cadmium dinonyl phosphorodithioate, and the zinc salt of aphosphorodithioic acid produced by the reaction of phosphoruspentasulfide with an equimolar mixture of isopropyl alcohol and n-hexylalcohol.

Many of the above-mentioned extreme pressure agents andcorrosion-oxidation inhibitors may also serve as antiwear agents. Zincdialkyl phosphorodithioates are examples of such multifunctionaladditives.

Pour point depressants may be used to improve low temperature propertiesof the oil-based compositions. Examples of useful pour point depressantsmay include polymethacrylates; polyacrylates; polyacrylamides;condensation products of haloparaffin waxes and aromatic compounds;vinyl carboxylate polymers; and terpolymers of dialkyl fumarates, vinylesters of fatty acids, alkyl vinyl ethers, or mixtures of two or morethereof.

The viscosity modifiers may include one or more polyacrylates,polymethacrylates, polyolefins, and/or styrene-maleic ester copolymers.

Anti-foam agents may be used to reduce or prevent the formation ofstable foam. The anti-foam agents may include silicones, organicpolymers, and the like.

The lubricant or functional fluid may include one or more thickeners toprovide the lubricant or functional fluid with a grease-likeconsistency. The thickener may comprise lithium hydroxide, lithiumhydroxide monohydrate, or a mixture thereof. The thickener may comprise9-decenoic acid diol.

The functional additives may be added directly to the lubricant orfunctional fluid composition. Alternatively, the additives may bediluted with a substantially inert, normally liquid organic diluent suchas mineral oil, naphtha, benzene, toluene or xylene, to form an additiveconcentrate, which may then be added to the lubricant and/or functionalfluid. These concentrates may contain from about 0.1 to about 99%, orfrom about 10% to about 90% by weight, of one or more of the additives.The remainder of the concentrate may comprise the substantially inertnormally liquid diluent.

This invention relates to a lubricant or functional fluid composition,comprising: an alcohol ester derived from the reaction of a malienatedmethyl 9-decenoate with iso-amyl alcohol; a polyalphaolefin; a hinderedaryl amine; and a polyisobutenyl succinic anhydride based dispersant.

The Fuel Composition

The fuel composition may contain a major proportion of a normally liquidfuel. The normally liquid fuel may comprise motor gasoline or a middledistillate fuel. The middle distillate fuel may comprise diesel fuel,fuel oil, kerosene, jet fuel, heating oil, naphtha, or a mixture of twoor more thereof. The fuel composition may also comprise one or morenon-hydrocarbonaceous materials such as alcohols, ethers, organo-nitrocompounds and the like (e.g., methanol, ethanol, diethyl ether, methylethyl ether, nitromethane). Normally liquid fuels which are mixtures ofone or more hydrocarbonaceous fuels and one or morenon-hydrocarbonaceous materials may be used. Examples of such mixturesmay include combinations of gasoline and ethanol, or combinations ofdiesel fuel and ether. Gasoline may comprise a mixture of hydrocarbonshaving an ASTM distillation range from about 60° C. at the 10%distillation point to about 205° C. at the 90% distillation point.

The normally liquid fuel may comprise a natural oil, including vegetableoil, animal fat or oil, or a mixture thereof. These may be referred toas biofuels or biodiesel fuels. The normally liquid fuel may comprise ahydrocarbon oil (e.g., a petroleum or crude oil distillate). The fuelmay comprise a mixture of a hydrocarbon oil and a natural oil.

The normally liquid fuel may comprise a synthetic fuel. The syntheticfuel may be derived from coal, natural gas, oil shale, biomass, or amixture of two or more thereof. The synthetic fuel may be derived from aFischer-Tropsch process.

The fuel composition may contain a property improving amount of one ormore of the above-described dispersants. This amount may be from about10 to about 1000 parts by weight, or from about 100 to about 500 partsby weight, of the dispersant per million parts of the normally liquidfuel.

The fuel composition may contain other additives well known to those ofskill in the art. These may include deposit preventers or modifiers suchas triaryl phosphates, dyes, cetane improvers, antioxidants such as2,6-di-tertiary-butyl-4-methyl-phenol, rust inhibitors such asalkenylsuccinic acids and anhydrides, bacteriostatic agents, guminhibitors, metal deactivators, demulsifiers, upper cylinder lubricants,anti-icing agents, mixtures of two or more thereof, and the like.

The fuel composition may further comprise a cold flow improver; additivefor increasing horsepower; additive for improving fuel economy; additivefor lubricating and reducing wear of engine components; additive forcleaning and preventing deposit buildup; additive for reducing smoke andparticulate emissions; additive for removing water; additive forreducing rust and corrosion; additive for upgrading and stabilizing thefuel; additive for improving storage and combustion capabilities;antioxidant; antistatic agent; corrosion inhibitor; fuel system icinginhibitor; cold flow improver; biocide; metal deactivator; additive forreducing fuel line and filter clogging; additive for improving fuelatomization; additive for reducing deposits on burner nozzles; additivefor enhancing flame stabilization; additive for improving combustion;additive for reducing soot formation; additive for neutralizing vanadiumand sodium; additive for improving heat transfer; additive for reducingthe formation of sulfur trioxide; additive for reducing stacktemperatures; additive for reducing carbon monoxide, oxygen and/orunburnt hydrocarbon in stack gases; additive for reducing fuelconsumption; polar compound for dispersing paraffins; oil-solubleamphiphile; pour point depressant; dewaxing additive; sludge inhibitor;dehazer; additive for reducing cloud point; or a mixtures of two or morethereof.

Functional Compositions

The functionalized or polyfunctionalized monomer or polymer may beuseful in polymer compositions or plastic formulations for makingextruded or molded articles, or for use in adhesives, coatingcompositions, including protective and/or decorative coatings (e.g.,paint), or for use in pharmaceuticals, cosmetics, personal careproducts, industrial cleaners, institutional cleaners, foods, beverages,oil filed chemicals, agricultural chemicals, and the like. The monomeror polymer may be partially or fully hydrogenated, depending on itsintended use.

The functional composition may further comprise one or more solvents(e.g., water or organic), thixotropic additives, pseudoplasticadditives, rheology modifiers, anti-settling agents, leveling agents,defoamers, pigments, dyes, plasticizers, viscosity stabilizers,biocides, viricides, fungicides, crosslinkers, humectants, surfactants,detergents, soaps, fragrances, sweetners, alcohol, food, food additives,mixtures of two or more thereof, and the like.

The thixotropic additive may comprise fumed silica and/or clay, and thelike. The leveling agent may comprise polysiloxane,dimethylpolysiloxane, polyether modified dimethylpolysiloxane, polyestermodified dimethylpolysiloxane, polymethylalkysiloxane, aralkyl modifiedpolymethylalkylsiloxane, alcohol alkoxylates, polyacrylates, polymericfluorosurfactants, fluoro modified polyacrylates, or a mixture of two ormore thereof.

The plasticizer may comprise ethylene glycol, polyethylene glycol,propylene glycol, polypropylene glycol, butane diol, polybutyleneglycol, glycerine, or a mixture of two or more thereof.

The viscosity stabilizer may comprise a mono or multifunctional hydroxylcompound. These may include methanol, ethanol, propanol, butanol,ethylene glycol, polyethylene glycol, propylene glycol, polyethyleneglycol, propylene glycol, polypropylene glycol, butane diol,polybutylene glycol, glycerine, or a mixture of two or more thereof.

The biocide, viricide or fungicide may comprise sodium hypochlorite,potassium hypochlorite, quaternary ammonium chloride, and the like.

The humectant may comprise polyacrylic acid, polyacrylic acid salt, anacrylic acid copolymer, a polyacrylic acid salt copolymer, or a mixtureof two or more thereof.

The surfactant may comprise one or more ionic and/or nonionic compounds.The ionic compounds may be cationic or amphoteric compounds. Thesurfactants that may be used may include alkanolamines,alkylarylsulfonates, amine oxides, poly(oxyalkylene) compounds,including block copolymers comprising alkylene oxide repeat units,carboxylated alcohol ethoxylates, ethoxylated alcohols, ethoxylatedalkyl phenols, ethoxylated amines and amides, ethoxylated fatty acids,ethoxylated fatty esters and oils, fatty esters, fatty acid amides,glycerol esters, glycol esters, sorbitan esters, imidazolinederivatives, lecithin and derivatives, lignin and derivatives,monoglycerides and derivatives, olefin sulfonates, phosphate esters andderivatives, propoxylated and ethoxylated fatty acids or alcohols oralkyl phenols, sorbitan derivatives, sucrose esters and derivatives,sulfates or alcohols or ethoxylated alcohols or fatty esters, sulfonatesof dodecyl and tridecyl benzenes or condensed naphthalenes or petroleum,sulfosuccinates and derivatives, and tridecyl and dodecyl benzenesulfonic acids. The surfactant may comprise sodium lauryl sulfonate,acetyltrimethyl ammonium bromide, and the like.

The concentration of each of the foregoing additives in the functionalcomposition may be up to about 25% by weight, or up to about 10% byweight, or up to about 5% by weight.

The functional composition, which may be in the form of a polymercomposition, may be provided in a solid form, e.g., powder, pellets, andthe like, or in a liquid form, optionally, with a solvent or vehicle.The solvent or vehicle may comprise an aqueous based solvent or vehicleor an organic solvent or vehicle. The organic solvent or vehicle maycomprise one or more alcohols, for example, methanol, ethanol, propanol,butanol, one or more ketones, for example, acetone, one or moreacetates, for example, methyl acetate, or a mixture of two or morethereof.

EXAMPLES

The following additional examples illustrate features in accordance withthe present invention, and are provided solely by way of illustration.They are not intended to limit the scope of the appended claims.

Example 5 Methyl 9-Decenoate Homopolymer Using t-Bu₂O₂

Methyl 9-decenoate (50 g, 0.271 mole) and di-t-butyl peroxide (4 g,0.0271 mole) are charged into a reaction flask that is equipped with athermometer, nitrogen inlet, magnetic stirrer, and reflux condenser. Theresulting reaction mixture is heated to 130° C. An exotherm occurs andthe temperature of the reaction mixture increases to 160° C. Theexotherm subsides over time and the reaction temperature is dropped to130° C. Heating is continued at 120-130° C. for 6.5 hrs. An additionalamount of di-t-butyl peroxide (4 g, 0.0271 mole) is added and thereaction mixture is heated for an additional time of 5 hrs. The reactionmixture is then stripped to 150° C. using vacuum of 2 torr (0.27kilopascal). Residue left after stripping, which is in the form of aviscous fluid, is the desired product. The amount of desired product is40 g (80% yield).

Example 6-9 Decenoic Acid Homopolymer Using t-Bu₂O₂

9-Decenoic acid (100 g, 0.59 mole) and di-t-butyl peroxide (8.6 g, 0.06mole) are charged into a 2-necked 250-mL flask that is equipped with amagnetic stirrer, Dean-Stark trap, nitrogen inlet, thermometer, andreflux condenser. The reaction mixture is heated to 130° C. An exothermoccurs and the temperature of the reaction mixture increases to 157° C.The exotherm subsides over time and the reaction temperature drops to130° C. Heating is continued at 120-130° C. for 6.5 hrs. The reactionmixture is then stripped at 150-180° C. using a vacuum of 2 torr (0.27kilopascal). Residue left after stripping, which is in the form of aviscous fluid, is the desired product. The amount of desired product is55 g (55% yield). The product has an acid number of 314 mg KOH/g.

Example 7 Homopolymerization of Pentaerythritol Ester of 9-Decenoic Acidby the Use of t-Bu₂O₂

Pentaerythritol ester of 9-decenoic acid (30 g, 0.04 mole) is chargedinto a 3-necked 100-mL flask that is equipped with a magnetic stirrer,nitrogen inlet, thermometer, and a reflux condenser. The ester is heatedto 150° C. and di-t-butyl peroxide (0.64 g, 0.0046 mole) is added in twoportions, 30 minutes apart. The reaction mixture is heated at 150° C.for 1 hr. The viscosity of the reaction mixture increases and polymer isformed.

Example 8 Copolymerization of 1-Decene and Pentaerythritol Ester of9-Decenoic Acid by the Use of t-Bu₂O₂

1-Decene (200 g, 1.43 moles) and pentaerythritol ester of 9-decenoicacid (40 g, 0.053 mole) are charged into a 3-necked 500-mL flask that isequipped with a magnetic stirrer, nitrogen inlet, thermometer, andreflux condenser. Di-t-butyl peroxide (20.8 g, 0.142 mole) is added infive portions that are 30 minutes apart. The reaction mixture is heatedat 130° C. for 10 hr. Distillation is then carried out to removeunreacted decene (122 g), leaving behind 130 g of a copolymer in theform of a clear viscous fluid.

Example 9 Copolymerization of 1-Decene and Methyl 9-Decenoate by the Useof t-Bu₂O₂

1-Decene (250 g, 1.786 mole), and methyl 9-decenoate (33 g, 0.179 mole)are charged into a 3-necked 500-mL flask that is equipped with amagnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap, andreflux condenser. The reaction mixture is brought to 150° C. anddi-t-butyl peroxide (32.5 g, 0.223 mole) is added in ten portions 30minutes apart. The reaction mixture is heated at 150° C. for a total of10 hr. Distillation is then carried out to remove the starting materialand low-boiling components, leaving behind 198 g of a clear viscousproduct (70% conversion).

Example 10 Copolymerization of 1-Decene and 9-Decenoic Acid by the Useof t-Bu₂O₂

1-Decene (200 g, 1.43 moles), and 9-decenoic acid (27 g, 0.159 mole) arecharged into a 3-necked 500-mL flask that is equipped with a magneticstirrer, nitrogen inlet, thermometer, and reflux condenser. The reactionmixture is brought to 150° C. and di-t-butyl peroxide (23.2 g, 0.159mole) is added in six portions that are 30 minutes apart. The reactionmixture is heated at 140° C. for 3 hr. Distillation is then carried outto remove the starting material and the low-boiling components, leavingbehind a clear viscous product that has an acid number of 60.

Example 11 Dispersants Derived from 1-Decene/9-Decenoic Acid Polymer

1-Decene (200 g, 1.43 moles), and 9-decenoic acid (27 g, 0.159 mole) arecharged into a 3-necked 500-mL flask that is equipped with a magneticstirrer, nitrogen inlet, thermometer, and reflux condenser. The reactionmixture is brought to 170° C. and di-t-amyl peroxide (27.5 g, 0.159mole) is added in six portions that are 30 minutes apart. The reactionmixture is heated at 150° C. for a total of 6.5 hr. Distillation iscarried out to remove the starting material and the low-boilingcomponents, leaving behind a clear viscous product that has an acidnumber of 56.

A first dispersant is made by reacting 50 g of the 1-decene/9-decenoicacid polymer with diethylenetriamine at 150° C. The carboxylic acid tonitrogen ratio is 2:3. The reaction mixture is held at this temperatureuntil the acid number of the mixture is 10. A small amount of toluene isused in the reaction to remove water of reaction. Toluene is removed atthe end of reaction.

A second dispersant is made by reacting 50 g of the 1-decene/9-decenoicacid polymer with pentaerythritol at 150° C. The carboxylic acid tohydroxyl ratio is 4:1. The reaction is continued until an acid number of10 is achieved. A small amount of toluene is used in the reaction toremove water of reaction. Toluene is removed at the end of reaction.

Both the first and second dispersants have good American PetroleumInstitute (API) Group I oil and Group II oil miscibility at 20 percentand 50 percent by weight.

Example 12 Polymerization of Methyl 9-Decenoate by the Use of an AcidCatalyst (Montmorillonite K10)

Methyl 9-decenoate (250 g) and Montmorillonite K10 (50 g) are placed ina glass liner. The glass liner is inserted in a Parr reaction vessel.The vessel is sealed, purged with N₂ for 15 minutes, and an initial N₂pressure of 8 psi (55.2 kilopascals) is applied. The mixture is heatedto 200° C. with 600 rpm stirring. The reaction mixture reaches thedesired temperature in 30 minutes. The reaction mixture is stirred atthis temperature for 8 hours. The final pressure is 135 psi (930.8kilopascals). The reaction mixture is hot-filtered to remove thecatalyst. The filtrate is subjected to vacuum distillation at 190° C.and 20 mmHg (2.67 kilopascals). The distillation residue (130 g) is thedesired product. The average molecular weight is about 500.

Example 13 Polymerization of 1-Decene-Methyl 9-Decenoate Mixture by theUse of an Acid Catalyst (Montmorillonite K10)

1-Decene (140 g, 1 mole), methyl 9-decenoate (184 g, 1 mole), andMontmorillonite K10 (50 g) are placed in a glass liner which is insertedin a Parr reaction vessel. The vessel is sealed, purged with N₂ for 15minutes, and an initial N₂ pressure of 8 psi (55.2 kilopascals) isapplied. The mixture is heated at 250° C. with 600 rpm stirring for 11hours. The final pressure is 135 psi (930.8 kilopascals). The reactionmixture is hot-filtered to remove the catalyst. The filtrate issubjected to vacuum distillation at 190° C. and 20 mmHg (2.67kilopascals). TLC and GC/MS indicate the presence of copolymer.

Example 14 Copolymerization of 1-Hexene and Methyl 9-Decenoate by theUse of t-Bu₂O₂

1-Hexene (150 g, 1.786 mole), and methyl 9-decenoate (33 g, 0.179 mole)are charged into a 3-necked 500-mL flask that is equipped with amagnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap, andreflux condenser. The reaction mixture is brought to 150° C. anddi-t-butyl peroxide (32.5 g, 0.223 mole) is added in ten portions 30minutes apart. The reaction mixture is heated at 150° C. for 10 hours.Distillation is then carried out to remove the starting material andlow-boiling components, leaving behind the desired product.

Example 15 Copolymerization of 1-Hexadecene and Methyl 9-Decenoate bythe Use of t-Bu₂O₂

1-Hexadecene (400 g, 1.786 mole), and methyl 9-decenoate (33 g, 0.179mole) are charged into a 3-necked 1 L-flask that is equipped with amagnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap, andreflux condenser. The reaction mixture is brought to 150° C. anddi-t-butyl peroxide (32.5 g, 0.223 mole) is added in ten portions 30minutes apart. The reaction mixture is heated at 150° C. for 10 hours.Distillation is carried out to remove the starting material andlow-boiling components, leaving behind the desired product.

Example 16 Copolymerization of 12-Tetraeicosene and Methyl 9-Decenoateby the Use of t-Bu₂O₂

12-Tetraeicosene (600 g, 1.786 mole), and methyl 9-decenoate (33 g,0.179 mole) are charged into a 3-necked 1 L-flask that is equipped witha magnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap, andreflux condenser. The reaction mixture is brought to 150° C. anddi-t-butyl peroxide (32.5 g, 0.223 mole) is added in ten portions 30minutes apart. The reaction mixture is heated at 150° C. for 10 hours.Distillation is carried out to remove the starting material andlow-boiling components, leaving behind the desired product.

Example 17 Copolymerization of 1-Decene and Methyl 5-Hexenoate by theUse of t-Bu₂O₂

1-Decene (250 g, 1.786 mole), and methyl 9-hexenoate (23 g, 0.179 mole)are charged into a 3-necked 500-mL flask that is equipped with amagnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap, andreflux condenser. The reaction mixture is brought to 130° C. anddi-t-butyl peroxide (32.5 g, 0.223 mole) is added in ten portions 30minutes apart. The reaction mixture is heated at 130° C. for 10 hours.Distillation is carried out to remove the starting material andlow-boiling components, leaving behind the desired product.

Example 18 Copolymerization of 1-Decene and Methyl 9-Octadecenoate bythe Use of t-Bu₂O₂

1-Decene (250 g, 1.786 mole), and methyl 9-octadecenoate (53 g, 0.179mole) are charged into a 3-necked 500-mL flask that is equipped with amagnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap, andreflux condenser. The reaction mixture is brought to 130° C. anddi-t-butyl peroxide (32.5 g, 0.223 mole) is added in ten portions 30minutes apart. The reaction mixture is heated at 130° C. for 10 hours.Distillation is carried out to remove the starting material andlow-boiling components, leaving behind the desired product.

Example 19 Copolymerization of 1-Hexadecene and Methyl 9-Octadecenoateby the Use of t-Bu₂O₂

1-Hexadecene (400 μg, 1.786 mole), and methyl 9-octadecenoate (53 g,0.179 mole) are charged into a 3-necked 1 L-flask that is equipped witha magnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap, andreflux condenser. The reaction mixture is brought to 150° C. anddi-t-butyl peroxide (32.5 g, 0.223 mole) is added in ten portions 30minutes apart. The reaction mixture is heated at 150° C. for 10 hours.Distillation is carried out to remove the starting material andlow-boiling components, leaving behind the desired product.

Example 20 Copolymerization of Dodecene and Methyl 9-Octadecenedioate bythe Use of t-Bu₂O₂

1-Dodecene (300 g, 1.786 mole), and methyl 9-octadecenedioate (63:6 g,0.179 mole) are charged into a 3-necked 500-mL flask that is equippedwith a magnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap,and reflux condenser. The reaction mixture is brought to 130° C. anddi-t-butyl peroxide (32.5 g, 0.223 mole) is added in ten portions 30minutes apart. The reaction mixture is heated at 130° C. for 10 hours.After this time, distillation is carried out to remove the startingmaterial and low-boiling components, leaving behind the desired product.

Example 21 Methyl 9-Decenoate Homopolymer Using t-Bu₂O₂

Methyl 9-decenoate (35 g, 0.271 mole) and di-t-butyl peroxide (4 g,0.0271 mole) are charged into a reaction flask that is equipped with athermometer, nitrogen inlet, magnetic stirrer, and reflux condenser.Reaction mixture is heated to 130° C. An exotherm occurs and thetemperature of the reaction mixture rises to 160° C. The exothermsubsides over time and the reaction temperature drops to 130° C. Heatingis continued at 120-130° C. for 6.5 hrs. An additional amount ofdi-t-butyl peroxide (4 g, 0.0271 mole) is added and the reaction mixtureis heated for an additional time of 5 hrs. The reaction mixture is thenstripped to 150° C. using vacuum of 2 torr (0.27 kilopascal) to yieldproduct in the form of a viscous fluid.

Example 22 5-Hexenoic Acid Homopolymer Using t-Bu₂O₂

5-Hexenoic acid (67 g, 0.59 mole) and di-t-butyl peroxide (8.6 g, 0.06mole) are charged into a 2-necked 250-mL flask that is equipped with amagnetic stirrer, Dean-Stark trap, nitrogen inlet, thermometer, andreflux condenser. The reaction mixture is heated to 130° C. An exothermoccurs and the temperature of the reaction mixture rises to 150° C. Theexotherm subsides over time and the reaction temperature drops to 130°C. Heating is continued at 120-130° C. for 6.5 hrs. The reaction mixtureis then stripped at 150-180° C. using vacuum of 2 torr (0.27kilopascals). Residue left after stripping, which is in the form of aviscous fluid, is the desired product.

Example 23 Methyl Octadecenoate Homopolymer Using t-Bu₂O₂

Methyl octadecenoate (81 g) and di-t-butyl peroxide (4 g) are chargedinto a reaction flask that is equipped with a thermometer, nitrogeninlet, magnetic stirrer, and reflux condenser. The reaction mixture isheated to 130° C. An exotherm occurs and the temperature of the reactionmixture rises to 160° C. The exotherm subsides over time and thereaction temperature drops to 130° C. Heating is continued at 120-130°C. for 6.5 hrs. An additional amount of di-t-butyl peroxide (4 g, 0.0271mole) is added and the reaction mixture is heated for an additional timeof 5 hrs. The reaction mixture is then stripped to 150° C. using avacuum of 2 torr (0.27 kilopascals) to yield the desired product whichis in the form of a viscous fluid.

Example 24 Octadecenoic Acid Homopolymer Using t-Bu₂O₂

Octadecenoic acid (79 g) and di-t-butyl peroxide (8.6 g) are chargedinto a 2-necked 250-mL flask that is equipped with a magnetic stirrer,Dean-Stark trap, nitrogen inlet, thermometer, and reflux condenser. Thereaction mixture is heated to 130° C. An exotherm occurs and thetemperature of the reaction mixture rises to 150° C. The exothermsubsides over time and the reaction temperature drops to 130° C. Heatingis continued at 120-130° C. for 6.5 hrs. The reaction mixture is thenstripped at 150-180° C. using vacuum of 2 torr (0.27 kilopascals).Residue left after stripping, which is in the form of a viscous fluid,is the desired product.

Example 25 Dispersant Preparation from 1-Decene/9-Decenoic Acid PolymerComposition

A 1-litre round-bottomed flask is charged with 400 g of a solution of75% polymer composition, prepared from a free radical polymerization of1-decene:9-decenoic acid (75:25) mole percent mixture, in xylenes. Thecontents of the flask are then heated with stirring to 175° C.Aminopropylimidazole (38 g) is added dropwise via a pressure equalizingdropping funnel over a period of 30 minutes. The reaction mixture isthen maintained at 175° C. with stirring and water removal for 3 hours.Solvent and low-boiling volatiles are removed via distillation, leavingbehind an amber viscous product that is filtered through a 12 mm Celitepad.

Example 26 Imide Dispersant Preparation from Methyl 9-DecenoateHomopolymer

A mixture of 500 g of homopolymer and 30 g of maleic anhydride is heatedto 110° C. This mixture is heated to 200° C. and is held there for 6 hr.The reaction mixture is then stripped of starting materials, leavingbehind succinated homopolymer. To this material is added 113 g ofmineral oil, and 10 g of a commercial mixture of ethylene polyamineshaving from about 3 to about 10 nitrogen atoms per molecule. Thereaction mixture is heated to 150° C. for 2 hr and is stripped byblowing with nitrogen. The reaction mixture is filtered to yield thefiltrate as an oil solution of the desired product.

Example 27 Dispersant Preparation from Methyl 9-Decenoate Homopolymer

A mixture of 500 g of methyl 9-decenoate homopolymer and 30 g of maleicanhydride is heated to 110° C. This mixture is heated to 200° C. and isheld there for 6 hr. After this time the reaction is stripped ofstarting materials, leaving behind succinated homopolymer. To thismaterial is added 30 g of pentaerythritol and the reaction mixture isheated to 210° C. and held at this temperature for 3 hr. The reactionmixture is cooled to 190° C. and 8 g of a commercial mixture of ethylenepolyamines having an average of about 3 to about 10 nitrogen atoms permolecule is added. The reaction mixture is stripped by heating at 205°C. with nitrogen blowing for 3 hours, then filtered to yield thefiltrate as an oil solution of the desired product.

Example 28 Detergent Preparation from 1-Decene/9-Decenoic Acid PolymerComposition

A mixture of 200 g of mineral oil, 30 g polyisobutenylsuccinic acidanhydride, 50 g of a mixture of 61% by weight isobutanol and 39% byweight amyl alcohol, and Mississippi Lime (86% available Ca) are chargedto a stainless steel reactor having a stirrer, condenser, and an oilsystem to a jacket around the reactor for both heating and cooling. Withstirrer agitation of the mixture and a nitrogen gas purge above thereaction mixture, 200 g of 1-decene/1-decenoic acid polymer composition,prepared from free radical polymerization of 1-decene:9-decenoic acid(75:25) mole percent mixture. The mixture is then heated to 90° C. tocomplete the acid and acid anhydride neutralization. 25 g methanol and140 g of the above-mentioned Mississippi Lime are added after coolingthe batch to 40° C. The material in the reaction vessel is carbonated at50-60° C. by passing carbon dioxide into the reaction mixture until thereaction mixture has a base number of approximately zero. Aftercarbonation, the material is flash dried to remove the alcohol promotersand water by raising the temperature to 150° C. and purging withnitrogen gas. The material is then cooled, solvent clarified by addingapproximately 150 parts hexane, and vacuum stripped of volatiles to 150°C. and 70 mm absolute Hg. The product is filtered and diluent oil isadded to adjust calcium content to 14.2 percent by weight calcium.

Example 29 Detergent Preparation from Methyl 9-Decenoate Homopolymer andAlkyl benzenesulfonic Acid Mixture

To a solution of 100 g of an alkylbenzenesulfonic acid, 100 g of methyl9-decenoate homopolymer, 10 g of polyisobutenylsuccinic anhydride, and50 g mineral oil is added 100 g of calcium hydroxide, and 50 g of amixture of 61 percent by weight isobutanol and 39 percent by weight amylalcohol. The temperature of the mixture increases to 89° C. over 10minutes due to an exotherm. During this period, the mixture is blownwith carbon dioxide at 4 cubic feet/hr (cfh) (113.3 liters per hour).Carbonation is continued for about 30 minutes as the temperaturegradually decreases to 74° C. The alcohols and other volatile materialsare stripped from the carbonated mixture by blowing nitrogen through itat 2 cfh (56.6 liters per hour) while the temperature is slowlyincreased to 150° C. over 90 minutes. After stripping is completed, theremaining mixture is held at 155-165° C. for about 30 minutes andfiltered to yield an oil solution of the desired basic detergent.

The following table shows data for homopolymers and various polymercompositions prepared using functionalized monomers in accordance withthe present teachings.

Viscosity Catalyst/Reaction Yield Measurement Monomer/s Temperature %(100° C.) Methyl 9- 10 m % Di-t-butyl 80 31.8 cPs; Decenoate peroxide 37cSt catalyst/130° C., 6.5 hrs.; then add another 10 m % initiator andheat at 130° C. for 5 hrs. 9-Decenoic 10 m % Di-t-butyl 55 Too viscousto Acid peroxide catalyst measure 130° C., 6.5 hrs., 1-Decene/ 10 m %Di-t-butyl 66 12 cPs; Methyl 9- peroxide catalyst; starts 14 cStDecenoate out at 150° C., then (9/1)m 135-140° C., 6.5 hrs. 1-Decene/ 10m % Di-t-butyl 64 12.8 cSt Methyl 9- peroxide catalyst Starts Decenoateout at 150 C., then 135-140° C., (9/1)m 10 hrs. 1-Decene/ 10 m %di-t-butyl 71 14 cSt Methyl 9- peroxide catalyst 150° C. Decenoate for10 hrs. (9/1)m 1-Decene/ 10 m % di-t-butyl 56 15.6 cPs Methyl 9-peroxide catalyst 135-140° C., Decenoate 6.5 hrs. (9/1)m 1-Decene/9- 10m% di-t-amyl 63 24 cPs Decenoic Acid peroxide catalyst, 140-150° C.,(9/1)m 6 hrs. 1-Decene/9- 30m % di-t-butyl 70 121 cPs Decenoic Acidperoxide catalyst, 135-140° C., (75/25)m 6.5 hrs. Pentaerythritol 10 m %di-t-butyl Unk. Polymer Ester of 9- peroxide catalyst Decenoic Acid 150°C., 1 hr. Pentaerythritol 10 m % di-t-butyl Unk. Very Viscous Ester of9- peroxide catalyst Fluid; 477 cPs Decenoic Acid 130° C., 8 hrs.1-Decene/ 10 m % di-t-butyl 65 50 cPs Pentaerythritol peroxide catalystEster of 9- 130° C., 10 hrs. Decenoic Acid (80:20)wt 1-Decene/9- 30m %di-t-butyl 75.5 49.5 cPs Decenoic Acid peroxide catalyst DTBP, (75:25))m135-140° C., 6.5 hrs.

Example 30

To a solution of maleinated methyl 9-decenoate (50.0 g, 0.535 mol),3-methyl-1-butanol (47.2 g, 0.535 mol), and Exxal 10 (84.7 g, 0.535 mol)in toluene (80 mL) p-toluenesulfonic acid (3.1 g, 0.016 mol) is added.The reaction is heated to reflux (120° C.) and azeotropic removal ofwater and methanol is performed using a Dean-Stark apparatus. After 5 h,the reaction is cooled to room temperature and diluted with ethylacetate (100 mL), washed with aqueous potassium hydroxide (0.07 M, 250mL), followed by water (2×250 mL). The organic phase is collected, driedover MgSO₄, filtered, and concentrated to a crude oil residue. Volatilesare removed by vacuum distillation (2 Torr, 140° C., 1.5 h) to yield thedesired product as a yellow oil (88.5 g). Product has kinematicviscosity of 5.8 cSt at 100° C. GC/MS (m/z) 496, 549.

Example 31

Maleinated methyl 9-decenoate (200 g, NNA=422 mg KOH/g) and Exxal 8(branched primary alcohol supplied by ExxonMobil) (100 g, 0.77 mol) arecharged into a reaction flask that is equipped with a thermocouple,nitrogen inlet, magnetic stirrer, and short-path distillation bridge.The mixture is heated to 80° C. and methanesulfonic acid (0.3 mol %, 70%aqueous solution) is added. The resulting reaction mixture is heated to100° C. The generated water is removed during distillation to drive thereaction to high conversion. The progress of the reaction is monitoredby acid value analysis. Once the distillation rate slows down thereaction temperature is increased. Heating is continued at 130-150° C.until water formation diminishes and the acid value reaches around 20.The reaction mixture is allowed to cool to 80° C. and vacuum (2 torr) isapplied to remove residual water and drive the reaction to an acid valueof <5. The temperature is increased stepwise to 160° C. to remove excessalcohol and other volatiles. The remaining ester product is filteredover a bed of silica (1 inch, fritted funnel) by applying vacuum. Thefiltration yields a golden to amber oil. The amount of desired productis 270 g (93% yield). Kinematic viscosity at 40° C.=51.28 cSt, at 100°C.=8.32, VI=136, and pour point=−39° C.

Example 32 Copolymerization of 1-Dodecene and Methyl 9-Decenoate by theUse of di-t-butyl Peroxide

1-Dodecene (128.27 g, 0.7261 mole), and methyl 9-decenoate (14.04 g,0.0762 mole) are charged into a 3-necked 250-mL flask that is equippedwith a magnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap,and reflux condenser. The reaction mixture is brought to 160° C. anddi-t-butyl peroxide (11.14 g, 0.0762 mole) is added in ten portions 30minutes apart. The reaction mixture is heated at 160° C. for a total of8.5 hr. Vacuum distillation to 200° C. is then carried out to remove theunreacted starting material and low-boiling components, leaving behind105.71 g of a clear viscous product (74% conversion). The kinematicviscosity at 100° C. is 22.09 cSt.

Example 33 Copolymerization of 1-Dodecene and Methyl 9-Decenoate by theUse of di-t-butyl Peroxide with Dodecanethiol Chain Transfer Agent

1-Dodecene (128.27 g, 0.7261 mole), methyl 9-decenoate (14.04 g, 0.0762mole), and dodecane thiol (0.5090 g, 0.0025 mole) are charged into a3-necked 250-mL flask that is equipped with a magnetic stirrer, nitrogeninlet, thermometer, Dean-Stark trap, and reflux condenser. The reactionmixture is brought to 160° C. and di-t-butyl peroxide (11.14 g, 0.0762mole) is added in ten portions 30 minutes apart. The reaction mixture isheated at 160° C. for a total of 8.5 hr. Vacuum distillation to 200° C.is then carried out to remove the unreacted starting material andlow-boiling components, leaving behind 92.36 g of a clear viscousproduct (65% conversion). The kinematic viscosity at 100° C. is 15.69cSt. Sulfur in the product is 847 ppm.

Example 34 Copolymerization of 1-Dodecene and Methyl 9-Decenoate by theUse of di-t-butyl Peroxide with t-nonyl Thiol Chain Transfer Agent

1-Dodecene (128.27 g, 0.7261 mole), methyl 9-decenoate (14.04 g, 0.0762mole), and t-nonyl thiol (0.4032 g, 0.0025 mole) are charged into a3-necked 250-mL flask that is equipped with a magnetic stirrer, nitrogeninlet, thermometer, Dean-Stark trap, and reflux condenser. The reactionmixture is brought to 160° C. and di-t-butyl peroxide (11.14 g, 0.0762mole) is added in ten portions 30 minutes apart. The reaction mixture isheated at 160° C. for a total of 8.5 hr. Vacuum distillation to 200° C.is then carried out to remove the unreacted starting material andlow-boiling components, leaving behind 73.54 g of a clear viscousproduct (50% conversion). The kinematic viscosity at 100° C. is 11.92cSt. Sulfur in the product is 927 ppm.

Example 35 Copolymerization of 1-Dodecene and Methyl 9-Decenoate by theUse of di-t-butyl Peroxide with Bromotrichloromethane Chain TransferAgent

1-Dodecene (128.27 g, 0.7261 mole), methyl 9-decenoate (14.04 g, 0.0762mole), and bromotrichloromethane (0.4986 g, 0.0025 mole) are chargedinto a 3-necked 250-mL flask that is equipped with a magnetic stirrer,nitrogen inlet, thermometer, Dean-Stark trap, and reflux condenser. Thereaction mixture is brought to 150° C. and di-t-butyl peroxide (11.14 g,0.0762 mole) is added in ten portions 30 minutes apart. The reactionmixture is heated at 150° C. for a total of 8.5 hr. Vacuum distillationto 200° C. is then carried out to remove the unreacted starting materialand low-boiling components, leaving behind 72.11 g of a clear yellowviscous product (51% conversion). The kinematic viscosity at 100° C. is11.31 cSt. Chlorine in the product is 2500 ppm

Example 36 Copolymerization of 1-Dodecene and Methyl 9-Decenoate by theUse of 2,5-dimethyl-2,5-di(t-butylperoxy)hexane

1-Dodecene (133.13 g, 0.7909 mole), methyl 9-decenoate (14.57 g, 0.0791mole), are charged into a 3-necked 250-mL flask that is equipped with amagnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap, andreflux condenser. The reaction mixture is brought to 150° C. and2,5-dimethyl-2,5-di(t-butylperoxy)hexane (10.52 g, 0.0362 mole) is addedin ten portions 30 minutes apart. The reaction mixture is heated at 150°C. for a total of 8.5 hr. Vacuum distillation to 200° C. is then carriedout to remove the unreacted starting material and low-boilingcomponents, leaving behind 94.79 g of a clear viscous product (64%conversion). The kinematic viscosity at 100° C. is 17.73 cSt.

Example 37 Copolymerization of 1-Dodecene and Methyl 9-Decenoate by theUse of di-t-amyl Peroxide

1-Dodecene (132.05 g, 0.7845 mole), methyl 9-decenoate (14.46 g, 0.0785mole), are charged into a 3-necked 250-mL flask that is equipped with amagnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap, andreflux condenser. The reaction mixture is brought to 150° C. anddi-t-amyl peroxide (13.09 g, 0.0751 mole) is added in ten portions 30minutes apart. The reaction mixture is heated at 150° C. for a total of8.5 hr. Vacuum distillation to 200° C. is then carried out to remove theunreacted starting material and low-boiling components, leaving behind114.72 g of a clear viscous product (78% conversion). The kinematicviscosity at 100° C. is 15.81 cSt.

Example 38 Copolymerization of 1-Dodecene and Methyl 9-Decenoate by theUse of t-butyl Peroxybenzoate

1-Dodecene (137.72 g, 0.8182 mole), methyl 9-decenoate (15.08 g, 0.0818mole), are charged into a 3-necked 250-mL flask that is equipped with amagnetic stirrer, nitrogen inlet, thermometer, Dean-Stark trap, andreflux condenser. The reaction mixture is brought to 150° C. and t-butylperoxybenzoate (15.32 g, 0.0788 mole) is added in ten portions 30minutes apart. The reaction mixture is heated at 150° C. for a total of8.5 hr. Vacuum distillation to 200° C. is then carried out to remove theunreacted starting material and low-boiling components, leaving behind97.83 g of a clear viscous product (64% conversion). The kinematicviscosity at 100° C. is 19.52 cSt.

Example 39

The following table shows the viscosity index for a series of polymerswith varying dodecene/9DAME ratios.

Dodecene/ Kinematic Kinematic Viscosity Poly- Methyl 9- Viscosity at100° C. Viscosity at 40° C. Index mer decenoate (cSt) (cSt) VI 1 95/5 22.30 157.70 169 2 75/25 20.77 146.90 165 3 50/50 20.34 141.46 167 425/75 21.49 159.49 160 5  0/100 23.17 177.85 158

Example 40

Reagent Mass Moles Equivalents 1-Dodecene 100.0 g 594 mmol 1.00 equiv9-DAME  11.0 g  60 mmol 0.10 equiv ^(n)Propanol  1.1 g (1.4 mL)  18 mmol 1.0 wt % BF₃  34.5 g 508 mmol 0.85 equiv

The reaction is conducted in a 500-mL borosilicate glass bubbler with asingle gas inlet and outlet. The reactor is equipped with a magneticstirrer. A thermometer is placed inside the reaction vessel fortemperature monitoring and a water bath is provided for external coolingof the reactor. The reactor outlet port is connected to a scrubber (tapwater) for the neutralization of the gaseous BF₃. Between the reactorand BF₃ lecture bottle, and scrubber and reactor, are situated dry trapsto prevent migration of material between apparatus due to potentialpressure changes. A borosilicate glass three-way valve is used toseparating N₂ and BF₃ inlet lines. The lecture bottle is fitted with a3000-psig connection-rated control valve for flow control. Tygon tubingis used for delivery of material between unit operations; Teflon tapesecures all tube-glassware junctions. 1-Dodecene, methyl 9-decenoate(9-DAME) and n-Propanol (1.1 g, 1.0 wt % versus olefins) are charged tothe reactor. The reactor contents are sparged with N₂ for 30 min, withmild agitation. N₂ sparge is discontinued, but inert atmospheremaintained. BF₃ is bubbled into the olefin-alcohol mixture for 2 h, at arate to maintain the temperature below 30° C. Maximum observed exothermis 29° C. The mass of BF₃ delivered is determined by mass difference atthe lecture bottle before and after the reaction. To terminate thereaction, BF₃ (g) feed is discontinued then N₂ sparging is carried outfor 30 min. Aqueous NH₄OH (8.27 M) is introduced into the reaction toquench residual BF₃ and BF₃.nPrOH complex; BF₃.NH₃ complex precipitatesas a white solid. 20 g MgSO₄ is added, the mixture stirred for 15 minthen solids are removed by filtration through a glass frit. The organicsobtained are submitted to vacuum distillation for the removal ofresidual monomer (170° C., 2 mmHg).

Results:

Mass In=100.0 g dodecene+11.0 g 9-DAME+1.1 g nPrOH+34.5 g BF₃=165.6 g

Mass Out=117 g reactor+27 g scrubber=144 g

% Mass Recovery=98%

98.5 g crude (1100-15-1) is submitted to vacuum distillation (170° C., 2mmHg). Bulk of distillate (38.6 g, 1100-15-3) is collected at 53-55° C.,2 torr). 59 g stripped material recovered as a pale yellow oil. 60%conversion.

Kinematic Viscosity (100° C.): 4.9 cSt

Kinematic Viscosity (40° C.): 21.5 cSt

VI: 160

IR: 1746 cm⁻¹ (ester resonance)

Example 41 Preparation of a Methyl 9-decenoate homo-oligomer Using BF₃

Reagent Mass Moles Equivalents 9-DAME 100.0 g 542 mmol 1.00 equiv^(n)Propanol  1.0 g (1.3 mL)  17 mmol  1.0 wt % BF₃  49.4 g 729 mmol1.34 equiv

Procedure:

The reaction is conducted in a 500-mL borosilicate glass bubbler with asingle gas inlet and outlet. The reactor is equipped with a magneticstirrer. A thermometer is placed inside the reaction vessel fortemperature monitoring and a water bath is provided for external coolingof the reactor. The reactor outlet port is connected to a scrubber(water, 250 mL) for the neutralization of the gaseous BF₃. Between thereactor and BF₃ lecture bottle, and scrubber and reactor, are situateddry traps to prevent migration of material between apparatus due topotential pressure changes. A borosilicate glass three-way valve is usedto separate N₂ and BF₃ inlet lines. The lecture bottle is fitted with a3000-psig connection-rated control valve for flow control. Tygon tubingis used for delivery of material between unit operations; Teflon tapesecured all tube-glassware junctions. Methyl 9-decenoate (9-DAME) andn-Propanol (1.0 wt % versus olefins) are charged to the reactor. Thereactor contents are sparged with N₂ for 30 min, with mild agitation. N₂sparge is discontinued, but inert atmosphere maintained. BF₃ is bubbledinto the olefin-alcohol mixture. To terminate the reaction, BF₃ (g) feedis discontinued then N₂ sparging is carried out for 60 min. The mass ofBF₃ delivered is determined by mass difference at the lecture bottlebefore the reaction and after the N₂ sparge. Pre- and post-reactionscrubber masses are obtained for mass balance purposes. To quenchresidual BF₃, BF₃.9-DAME and BF₃.nPrOH complexes, aqueous ammonia (8.27M) is introduced into the reaction. The resulting emulsion is extractedwith 50% EtOAc in hexanes, dried (MgSO₄) and submitted to vacuumdistillation for the removal of residual monomer (175° C., 2 mmHg, 90min).

Results:

Mass In=100.0 g 9-DAME+1.0 g nPrOH+49.4 g BF₃=150.4 g

Mass Out=138.4 g reactor+9.7 g scrubber=148.1 g

% Mass Balance=98%

66.1 g crude (1100-24-1) is submitted to vacuum distillation (175° C., 2mmHg). Bulk of distillate (17.3 g, 1100-24-3) is collected at 78-84° C.(2 torr). 48.8 g of residual material (1100-24-2) is recovered.Conversion=73.5%. Yield=49%.

GC-MS of 1100-24-3: 9-DAME isomers (5 peaks of MW=184, retention timesfrom 4.81-5.25 min).

Kinematic Viscosity (100° C.): 6.7 cSt

Kinematic Viscosity (40° C.): 33.2 cSt

VI: 164

Pour point: <−45° C.

Aniline point: Miscible at ambient temperature.

Noack volatility: 8.75% (Hategan on Mar. 1, 2012)

Example 42 Preparation of a 9-DAME/1-Dodecene Oligomer (1:4) Using BF₃(No Solvent)

Reagent Mass Moles Equivalents 1-Dodecene 300.0 g  1782 mmol 1.00 9-DAME67.7 g  356 mmol 0.20 ^(n)Propanol 3.65 g  61 mmol 1.0 wt % BF₃ 38.8 gmmol Equiv

Procedure:

The reaction is conducted in a 4-neck 1-L resin kettle equipped with asingle gas inlet and outlet tube and a thermocouple. Unused ports areclosed with glass stoppers. A perfluoropolymer O-ring is used at headand kettle juncture. The reactor is equipped with a magnetic stirrer anda 15-20° C. water bath is provided for external cooling of the reactor.The reactor outlet is connected to a scrubber (water, 200 mL) for theneutralization of the gaseous BF₃. Between the reactor and BF₃ lecturebottle, and scrubber and reactor, are situated 1 L dry traps to preventmigration of material between apparatus due to potential pressurechanges. A borosilicate three-way valve is used to separate BF₃ and N₂inlets. The lecture bottle is fitted with a 3000-psig connection-ratedcontrol valve for flow control. Tygon tubing is used for delivery ofmaterial between unit operations; Teflon tape secured all tube-glasswarejunctions. 1-dodecene, methyl 9-decenoate (9-DAME) and n-Propanol (1.0wt % versus olefins) were charged to the reactor. The reactor contentswere sparged with N₂ for 30 min, with stirring. N₂ sparge isdiscontinued, but inert atmosphere maintained. BF₃ is bubbled into theolefin-alcohol mixture. To terminate the reaction, BF₃ (g) feed isdiscontinued then N₂ sparging is carried out for 60 min. The mass of BF₃delivered is determined by mass difference at the lecture bottle beforethe reaction and after the N₂ sparge. Pre- and post-reaction scrubbermasses are obtained for mass balance purposes. To quench residual BF₃,BF₃-9-DAME and BF₃.nPrOH complexes, aqueous ammonia (8.27 M) isintroduced into the reaction; an exothermic reaction is cooled on a roomtemperature water bath. The resulting emulsion is treated with 40 gMgSO₄, stirred for 30 min then filtered through a glass sintered funnel.The crude material is submitted to vacuum distillation for the removalof residual monomer (175° C., 2 mmHg, 90 min).

Results:

299.5 g crude is submitted to vacuum distillation (175° C., 2 mmHg).Bulk of distillate (109.8 g, 1100-28-3) is collected at 78-84° C. (2torr). 184.9 g of residual material (1100-28-2) is recovered.

Conversion=62%. Isolated yield=50%.

Kinematic Viscosity (100° C.): 4.30 cSt; Kinematic Viscosity (40° C.):18.58 cSt; VI: 143

Pour point: −36° C.

Aniline point: 68° C.

Noack volatility: 15.2%

Example 43 Post-Oligomerization Recovery of BF₃ as a Mixed Alcohol(MeOH.nPrOH) Complex Via Vacuum Distillation

Reagent Mass Moles Equivalents 9-DAME 18.4 g 100 mmol 1.0 BF₃•nPrOHcomplex 14.0 g 110 mmol 1.1Purpose: To determine if BF₃.nPrOH complex can be separated from anoligomerization reaction via distillation under reduced pressure.

Procedure:

The reaction is conducted in a 3-neck 50-mL round bottom flask equippedwith gas inlet and outlet tubes and digital thermocouple. The reactor isequipped with a magnetic stirrer, and a 3° C. water bath is provided forexternal cooling. The reactor outlet is connected to a scrubber (water,679 g) for the neutralization of any liberated gaseous BF₃. Between thereactor and BF₃ lecture bottle, and scrubber and reactor, are situated250 mL dry traps. These are used to prevent migration of materialbetween apparatus due to potential pressure changes. A borosilicateglass three-way valve is used to separate BF₃ and N₂ inlet lines. Thelecture bottle is fitted with a 3000-psig connection-rated control valvefor flow control. Tygon tubing is used for delivery of material betweenunit operations; Teflon tape secures all tube-glassware junctions.BF₃.nPrOH complex (1100-33) is charged to the reactor. The reactorcontents are purged with N₂ for 30 min, with stirring. 9-DAME is thenintroduced to the reactor, dropwise via syringe. An exothermic reactionis observed; the rate of ester addition is controlled such that thereaction temperature does not exceed 10° C. After 2 at 2° C. then 1 h atambient temperature, N₂ sweep is discontinued and a short pathdistillation head placed on the reactor. (The reaction is stillproceeding at this time, but prematurely processed for timeconstraints.) Vacuum distillation of the orange reaction solutionfollowed (to 175° C./3 torr).

Results:

Two species are collected in the distillation receiver, forming twoliquid phases. The top phase is colorless and clear and the bottom (15.3g), clear and orange-red. The residue in the distillation pot (5.8 g) islight orange and clear (dark amber, mid-distillation).

The two distillates are separated, with trace bottom materialcontaminating the top phase. BF₃ content is determined qualitatively inthe distillation residue (oligomer) and top phase. Aqueous ammonia istitrated into each sample; no precipitate (BF₃.NH₃) forms in thedistillation residue. 1.8 g 29% aq. ammonia (14 mmol) is added to thetop layer distillate to achieve a colorless supernatant liquid andprecipitate BF₃—NH₃.

The mass balance of materials in/out suggests that the bottom distillatelayer contains the bulk of BF₃ (˜96 mmol) from the reaction pot. Theefficacy of the recovered catalyst complex is investigated.

Mass In=18.4 g 9-DAME+13.8 g BF₃.nPrOH=32.2 g

Mass Out=5.8 g 1100-34-2+11.4 g 1100-34-3-top+13.0 g 1100-34-3-bot=30.2g

% Mass Balance=94%

Isolated yield (oligomer)=31%.

Recovered BF₃.ROH=94%

Example 44

A solution of 9-decenoic acid methyl ester (65.6 g, 0.356 mol),1-dodecene (60.0 g, 0.357 mol), and 1-butanol (1.20 g, 16.2 mmol) in30.0 mL of 1,2-dichloroethane is placed in a water bath and is spargedwith nitrogen for 25 min. Boron trifluoride (59.6 g, 0.879 mol) issparged into the stirred solution over a period of 3.5 hours. During thecourse of the reaction, the temperature increases from 20 to 58° C. overa period of 15 minutes, then slowly returned to 22° C. over a period ofthree hours. After sparging with boron trifluoride is complete, thereaction mixture is sparged with nitrogen for 45 minutes. The reactionis quenched by slow addition of 35 mL of concentrated (28-30%) aqueousover 15 min. The organic layer is collected, dried with MgSO₄, filtered,and concentrated via rotary evaporation. The filtrate is distilled (2Torr, 175° C., 1.5 h) to give 66.7 g (53% yield) of a pale yellow oil.Kinematic Viscosity (100° C.)=4.23 cSt., Kinematic Viscosity (40°C.)=20.72 cSt., VI=108, Acid value=0.89, Noack (TGA)=20.1%. The productis soluble as a 60:40 blend in PAO4.

Example 45

A solution of 9-decenoic acid methyl ester (32.9 g, 0.178 mol),1-dodecene (150.0 g, 0.891 mol), and 1-propanol (1.82 g, 30.3 mmol) in30.0 mL of 1,2-dichloroethane is placed in a water bath and is spargedwith nitrogen for 20 min. Boron trifluoride (24.0 g, 0.354 mol) issparged into the stirred solution over a period of 3.0 hours. During thecourse of the reaction, the temperature increases from 18 to 40° C. overa period of 35 minutes, then slowly returned to 23° C. over a period of2.5 hours. After sparging with boron trifluoride is complete, thereaction vessel is sealed, and the mixture is stirred for an additional1 hour before being sparged with nitrogen for 45 minutes. The reactionis quenched by slow addition of 20 mL of concentrated (28-30%) aqueousover 15 min. The organic layer is collected, dried with MgSO₄, filtered,and concentrated via rotary evaporation. The filtrate is distilled (2Torr, 175° C., 1.5 h) to give 124.4 g (68% yield) of a pale yellow oil.Kinematic Viscosity (100° C.)=4.16 cSt., Kinematic Viscosity (40°C.)=18.07 cSt., VI=137, Noack (TGA)=18.6%, aniline point=70° C.

Example 46

To a suspension of aluminum chloride (8.33 g, 62.5 mmol) in 40 mL ofheptane at 20° C. is added a solution of 9-decenoic acid methyl ester(9.21 g, 50 mmol) and 1-decene (70.1 g, 500 mmol) at a rate thatmaintained the internal temperature at 25±1° C. over 1.5 h. Uponcomplete addition, the reaction mixture is stirred for 2 h at 20-25° C.Water (15 mL, 0.83 mol) is added slowly to the reaction mixture inportions over 30 min, maintaining the temperature between 20-25° C. Themixture is stirred for 0.5 h and then allowed to stand for 1 h. Theorganic layer is decanted and the remaining residue is rinsed threetimes with 15 mL each heptane. The combined organic-layers are stirredwith NaHCO3 (50 g, 0.6 mol) for 30 min. The mixture is filtered and thefiltrate is concentrated on a rotovap. The resulting oil is distilledunder vacuum (2 Torr, 175° C., 1 h) to give 66 g (83% yield) of a paleyellow oil. Kinematic Viscosity (100° C.) 69.5 cSt. IR (cm⁻¹) 1746.

Example 47

To a suspension of aluminum chloride (8.33 g, 62.5 mmol) in 40 mL ofheptane at 80° C. is added a solution of 9-decenoic acid methyl ester(9.21 g, 50 mmol) and 1-decene (70.1 g, 500 mmol) at a rate thatmaintains the internal temperature at 85-90° C. over 0.5 h. Uponcomplete addition, the reaction mixture is stirred for 2 h at 85° C.Water (15 mL, 0.83 mol) is added slowly to the reaction mixture inportions over 30 min, maintaining the temperature between 25-30° C. Themixture is stirred for 0.5 h and then allowed to stand for 1 h. Theorganic layer is decanted and the remaining residue is rinsed threetimes with 15 mL each heptane. The combined organic layers were stirredwith NaHCO3 (50 g, 0.6 mol) for 30 min. The mixture is filtered and thefiltrate is concentrated on a rotovap. The resulting oil is distilledunder vacuum (2 Torr, 175° C., 1 h) to give 64 g (81% yield) of a paleyellow oil. Kinematic Viscosity (100° C.) 25 cSt.

Example 48

To a suspension of aluminum chloride (8.33 g, 62.5 mmol) in 40 mL ofoctane at 110° C. is added a solution of 9-decenoic acid methyl ester(9.21 g, 50 mmol) and 1-decene (70.1 g, 500 mmol) at a rate thatmaintains the internal temperature at 115-120° C. over 0.5 h. Uponcomplete addition, the reaction mixture is stirred for 2 h at 115° C.Water (15 mL, 0.83 mol) is added slowly to the reaction mixture inportions over 30 min, maintaining the temperature between 25-30° C. Themixture is stirred for 0.5 h and then allowed to stand for 1 h. Theorganic layer is decanted and the remaining residue is rinsed threetimes with 15 mL each heptane. The combined organic layers were stirredwith NaHCO3 (50 g, 0.6 mol) for 30 min. The mixture is filtered and thefiltrate is concentrated on a rotovap. The resulting oil is distilledunder vacuum (2 Torr, 175° C., 1 h) to give 61 g (77% yield) of a paleyellow oil. Kinematic Viscosity (100° C.) 18.8 cSt.

Example 49

A solution of 9-decenoic acid methyl ester (200 g, 1.09 mol), 1-dodecene(200 g, 1.19 mol), and 1-butanol (4.0 g, 0.054 mol) is cooled to 10° C.and sparged with nitrogen for 15 min. Boron trifluoride is sparged intothe stirred solution while the temperature is maintained near 30° C. Thetemperature spiked briefly to 45° C. when the solution becomessupersaturated with boron trifluoride. After 4 h sparging with borontrifluoride the reaction mixture is sparged with nitrogen for 1.5 h. Theamount of boron trifluoride contained in the reaction mixture is 77.7 g(1.15 mol). The reaction mixture is cooled to 10° C. and treated with 98mL (1.37 mol) of concentrated (28-30%) aqueous ammonia portionwise overabout 15 min. The mixture is stirred for 15 min, treated with 50 g ofMgSO4, and filtered. The filtrate is distilled (2 Torr, 190° C., 0.5 h)to give 258 g (65% yield) of a pale yellow oil. Kinematic Viscosity(100° C.)=4.7 cSt.

The properties for various functional base oils of the invention areshown in the tables below.

PDSC Oxidation PDSC Apparent Viscosity CCS CCS CCS CCS CCS D6186Oxidation Noack Viscosity @ D445 D5293 D5293 D5293 D5293 D5293 200 C.E2009 Volatility 150 C. 100 C. −15 C. −20 C. −25 C. −30 C. −35 C. OITOOT D5800 D4683 Iodine Product (cSt) (cp) (cp) (cp) (cp) (cp) (min.) (°C.) (wt %) (cP) value API Group III Oil 6.2 946 1572 2667 4855 8796 2.18API Group II Oil 10.2 3548 6384 12609 29361 80028 PAO10(Polyalphaolefin) 10 1965 3195 5296 9324 197 3.23 Esterx NP451(Synthetic 5 2363 Ester) 1-Dodecene/Methyl 9- 22.3 6072 9914 17037 95222.6 193 2.4 8 decenoate(10:1)m 1-Dodecene/Methyl 9- 22.4 51971 decenoate(10:1)m 1-dodecene/9-DAME 24.6 14971 (10:1)m t-butyl cat 8.3%1-dodecene/9-DAME 23.4 5260 8558 14521 (3:1)m t-butyl cat 8.5%1-Dodecene/Methyl 9- NA 11901 20732 36436 decenoate (1:1)m1-Decene/1-Dodecene(1:1)m/ 20.4 23891 Methyl 9-decenoate (10:1)m1-Decene/1-Dodecene/ 21.8 5136 8296 13960 Methyl 9-decenoate (10:1:1)mt-butyl cat 8.3% 1-Decene/Methyl 9- 13.0 2496 3972 6516 11351 22211 4.2330 decenoate (10:1)m 1-Decene/Methyl 9- 17.7 4617 13078 46467 2.4 1943.6 18 decenoate (10:1)m 1-Decene/Methyl 9- 17.8 4350 7065 12006decenoate (3:1)m t-butyl cat 8.5% 1-Decene/Methyl 9- 16.0 50868 2.0 1733.0 decenoate (1:1)m 1-Decene/Methyl 9- 28.8 10871 19037 33812 decenoate(1:1)m 1-Octene/Methyl 9- 13623 decenoate (10:1)m 1-Decene/Methyl 9-35725 decenoate/Dimethylamide 1-Dodecene/Methyl 9- 4.8 1050 1 189decenoate (10:1) BF₃ catalyst Maleinated methyl 9- 10.5 9700 0.1 187decenoate - 3,5,5 tri- methylhexanol ester Maleinated methyl 9- 6.0 49630.2 190 decenoate - iso-amyl alcohol ester Maleinated methyl 9- 7.110420 0.5 0.191 decenoate - 2-ethyl- hexanol ester Maleinated Methyl 9-8.3 41721 decenoate- Exxal 8 ester API Group III Oil 6.2 946 1572 26674855 8796 2.18 API Group II Oil 10.2 3548 6384 12609 29361 80028 PAO10(Polyalphaolefin) 10 1965 3195 5296 9324 197 3.23 Esterx NP451(Synthetic 5 2363 Ester) 1-Dodecene/Methyl 9- 22.3 6072 9914 17037 95222.6 193 2.4 8 decenoate(10:1)m 1-Dodecene/Methyl 9- 22.4 51971 decenoate(10:1)m 1-dodecene/9-DAME 24.6 14971 (10:1)m t-butyl cat 8.3%1-dodecene/9-DAME (3:1)m 23.4 5260 8558 14521 t-butyl cat 8.5%1-Dodecene/Methyl 9- NA 11901 20732 36436 decenoate (1:1)m1-Decene/1-Dodecene(1:1)m/ 20.4 23891 Methyl 9-decenoate (10:1)m1-Decene/1-Dodecene/ 21.8 5136 8296 13960 Methyl 9-decenoate (10:1:1)mt-butyl cat 8.3% 1-Decene/Methyl 9- 13.0 2496 3972 6516 11351 22211 4.2330 decenoate (10:1)m 1-Decene/Methyl 9- 17.7 4617 13078 46467 2.4 1943.6 18 decenoate (10:1)m 1-Decene/Methyl 9- 17.8 4350 7065 12006decenoate (3:1)m t-butyl cat 8.5% 1-Decene/Methyl 9- 16.0 50868 2.0 1733.0 decenoate (1:1)m 1-Decene/Methyl 9- 28.8 10871 19037 33812 decenoate(1:1)m 1-Octene/Methyl 9- 13623 decenoate (10:1)m 1-Decene/Methyl 9-35725 decenoate/Dimethylamide 1-Dodecene/Methyl 9- 4.8 1050 1 189decenoate (10:1) BF3 catalyst Maleinated methyl 9- 10.5 9700 0.1 187decenoate - 3,5,5 tri- methylhexanol ester Maleinated methyl 9- 6.0 49630.2 190 decenoate - iso-amyl alcohol ester Maleinated methyl 9- 7.110420 0.5 0.191 decenoate - 2-ethyl- hexanol ester Maleinated Methyl 9-8.3 41721 decenoate - Exxal 8 ester

While the invention has been explained in relation to variousembodiments, it is to be understood that various modifications thereofwill become apparent to those skilled in the art upon reading thespecification. Therefore, it is to be understood that the inventiondisclosed herein includes any such modifications that may fall withinthe scope of the appended claims.

1. A malienated derivative composition derived from: (i) afunctionalized monomer comprising a hydrocarbyl group with one or morecarbon-carbon double bonds and one or more functional groups attached tothe hydrocarbyl group, the hydrocarbyl group containing at least about 5carbon atoms, the functional group comprising a carboxylic acid group ora derivative thereof, a hydroxyl group, an amino group, a carbonylgroup, a cyano group, a salt group, an amide salt group, an ester saltgroup, or a mixture of two or more thereof; (ii) maleic anhydride; and(iii) a nitrogen-containing reagent, an oxygen-containing reagent, ametal, a metal compound, or a mixture of two or more thereof.
 2. Thecomposition of claim 1 wherein the functionalized monomer is reactedwith the maleic anhydride to form an intermediate product, and theintermediate product is then reacted with the nitrogen-containingreagent, oxygen containing reagent, metal and/or metal compound to formthe malienated derivative composition.
 3. The composition of claim 1wherein the nitrogen-containing reagent, oxygen-containing reagent,metal and/or metal compound is reacted with the maleic anhydride to forman intermediate product, and the intermediate product is then reactedwith the functionalized monomer to form the malienated derivativecomposition.
 4. The composition of claim 1 wherein the functionalizedmonomer comprises an unsaturated carboxylic acid, anhydride, ester,amide, imide, alcohol, amine, aldehyde, ketone, nitrile, salt, amidesalt, ester salt, or a mixture of two or more thereof.
 5. Thecomposition of claim 1 wherein the malienated derivatize comprises anamide, imide, diamide, ester, di-ester, salt, metal salt, amine salt,amide salt, ester salt, or a mixture of two or more thereof.
 6. Thecomposition of claim 1 wherein the hydrocarbyl group contains one, two,three or four carbon-carbon double bonds.
 7. The composition of claim 1wherein the functionalized monomer contains a carbon-carbon double bondin the terminal position of the hydrocarbyl group.
 8. The composition ofclaim 1 wherein the functional group is attached to a terminal carbonatom on the hydrocarbyl group.
 9. The composition of claim 1 wherein thefunctional group is attached to an internal carbon atom in thehydrocarbyl group.
 10. The composition of claim 1 wherein thefunctionalized monomer comprises methyl 9-decenoate.
 11. The compositionof claim 1 wherein the nitrogen-containing reagent comprises ammonia, anamine containing one or more primary and/or secondary amino groups, amono-substituted amine, di-substituted amine, an amino-alcohol, an amineterminated poly(oxyalkylene) or a mixture of two or more thereof. 12.The composition of claim 1 wherein the nitrogen-containing reagentcomprises methylamine, dimethylamine, ethylamine, diethylamine,propylamine, dipropylamine, butylamine, dibutylamine, pentylamine,dipentylamine, hexylamine, dihexylamine, heptylamine, diheptylamine,octylamine, dioctylamine, methanolamine, dimethanolamine, ethanolamine,diethanolamine, propanolamine, dipropanolamine, butanolamine,dibutanolamine, pentanolamine, dipentanolamine, hexanolamine,dihexanolamine, heptanolamine, diheptanolamine, octanolamine,dioctanolamine, aniline, ethylenediamine, 1,3-propanediamine,1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine,1,7-heptanediamine, 1,8-octanediamine, 1,3-bis(aminomethyl)cyclohexane,meta-xylenediamine, 1,8-naphthalenediamine, p-phenylenediamine,N-(2-aminoethyl)-1,3-propanediamine, diethylenetriamine,dipropylenetriamine, dibutylenetriamine, dipentylenetriamine,dihexylenetriamine, diheptylenetriamine, dioctylenetriamine, spermidine,melamine, triethylenetetramine, tripropylenetetramine,tributylenetetramine, tripentylenetetramine, trihexylenetetramine,triheptylenetetramine, trioctylenetetramine, hexamine, an imidazole,aminopropylimidazole, oxazolidine, or a mixture of two or more thereof.13. The composition of claim 1 wherein the nitrogen-containing reagentcomprises a polyamine represented by the formula

wherein each R is independently hydrogen, a hydrocarbyl group or ahydroxy-substituted hydrocarbyl group containing up to about 30 carbonatoms, with the proviso that at least one R is hydrogen, n is a numberin the range from 1 to about 10, and R¹ is an alkyene group containing 1to about 18 carbon atoms.
 14. The composition of claim 1 wherein thenitrogen-containing reagent comprises methylene polyamine, ethylenepolyamine, propylene polyamine, butylenes polyamine, pentylenepolyamine, hexylene polyamine, heptylene polyamine, ethylene diamine,triethylene tetramine, tris(2-aminoethyl)amine, propylene diamine,trimethylene diamine, hexamethylene diamine, decamethylene diamine,octamethylene diamine, di(heptamethylene)triamine, tripropylenetetramine, tetraethylene pentamine, trimethylene diamine, pentaethylenehexamine, di(trimethylene)triamine,2-heptyl-3-(2-aminopropyl)imidazoline, 1,3-bis(2-amino-ethyl)piperazine,1,4-bis(2-aminoethyl)piperazine, 2-methyl-1-(2-aminobutyl)piperazine, ora mixture of two or more thereof.
 15. The composition of claim 1 whereinthe oxygen-containing reagent comprises methanol, ethanol, propanol,butanol, pentanol, hexanol, heptanol, octanol, decanol, dodecanol,tetradecanol, hexadecanol, octadecanol, isopropanol, isobutanol,sec-butanol, tert-butanol, isopentanol, amyl alcohol, tert-pentanol,cyclopentanol, cyclohexanol, 2-ethylhexanol, allyl alcohol, crotylalcohol, methylvinyl carbinol, benzyl alcohol, alpha-phenylethylalcohol, beta-phenylethyl alcohol, diphenylcarbinol, triphenylcarbinol,cinnamyl alcohol, or a mixture of two or more thereof.
 16. Thecomposition of claim 1 wherein the oxygen-containing reagent comprisesone or more polyols containing from 2 to about 10 carbon atoms, and from2 to about 6 hydroxyl groups.
 17. The composition of claim 1 wherein theoxygen-containing reagent comprises ethylene glycol, glycerol,trimethylolpropane, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol,1,3-butanediol, 2,3-butanediol, 2-ethyl-1,3-propanediol,2-ethyl-2-butyl-1,3-propanediol, neopentyl glycol,2,2,4-trimethyl-1,3-pentanediol, pentaerythritol, sorbitol, or a mixtureof two or more thereof.
 18. The composition of claim 1 wherein the metalis an alkali metal, an alkaline earth metal, Group IIIA metal, Group IVAmetal, Group VA metal, transition metal, lanthanide series metal,actinides series metal, or a mixture of two or more thereof.
 19. Thecomposition of claim 1 wherein the metal is Li, Na, K, Rb, Be, Mg, Ca,Sr, Ba, B, Al, Ga, In, Sn, Pb, Sb, Bi, Sc, Ti, V, Cr, Mn, Fe, Co, Ni,Cu, Zn, Zr, Mo, Ru, Rh, Pd, Ag, Cd, or a mixture of two or more thereof.20. The composition of claim 1 wherein the metal comprises an alkalimetal, alkaline earth metal, titanium, zirconium, molybdenum, iron,copper, aluminum, zinc, or a mixture of two or more thereof.
 21. Thecomposition of claim 1 wherein the functionalized monomer and maleicanhydride are reacted to form a malienated functionalized monomer andthe malienated functionalized monomer and an alkenyl succinic anhydrideare reacted with the nitrogen-containing reagent and/oroxygen-containing reagent.
 22. The composition of claim 21 wherein thealkenyl succinic anhydride comprises a polyisobutenyl succinicanhydride.
 23. The composition of claim 1, wherein the functionalizedmonomer is reacted with the maleic anhydride to form a malienatedfunctionalized monomer, and the malienated functionalized monomer isreacted with the nitrogen-containing reagent and/or oxygen containingreagent to form the dispersant composition.
 24. The composition of claim23 wherein the dispersant is mixed with a succinimide.
 25. Thecomposition of claim 24 wherein the succinimide is a polyisobutenylsuccinimide.
 26. A detergent composition comprising a neutral oroverbased detergent derived from the composition of claim 1 wherein themaleic anhydride is reacted with the functionalized monomer and a metalor metal compound.
 27. The detergent composition of claim 26 wherein themetal comprises an alkali metal, alkaline earth metal, titanium,zirconium, molybdenum, iron, copper, aluminum, zinc, or a mixture of twoor more thereof.
 28. The detergent composition of claim 26 wherein oneor more alkaryl sulfonic acids are mixed with the malienate derivative.29. The detergent composition of claim 28 wherein the alkaryl sulfonicacid is alkylbenzene sulfonic acid.
 30. The detergent composition ofclaim 26 wherein the detergent is derived from (1) the reaction productof the functionalized monomer with maliec anhydride, optionally, incombination with an alkarylsulfonic acid, and (2) a reaction medium, (3)a stoichiometric excess of the metal or metal compound, (4) a promoter,and (5) an acidic material.
 31. The detergent composition of claim 26wherein the detergent comprises a boron-containing overbased detergentcomposition.
 32. A concentrate composition comprising from about 0.1% toabout 99% by weight of the composition of claim 1, and a normally liquiddiluent.
 33. A lubricant or functional fluid composition comprising thecomposition of claim
 1. 34. The lubricant or functional fluidcomposition of claim 33 wherein the composition further comprises an APIGroup I, Group II, Group III, Group IV, Group V base oil, natural oil,estolide, or a mixture of two or more thereof.
 35. The lubricant orfunctional fluid composition of claim 33 wherein the lubricant orfunctional fluid composition further comprises a supplemental detergent,supplemental dispersant, corrosion inhibitor, oxidation inhibitor,antiwear agent, friction modifier, pourpoint depressant, anti-foamagent, metal deactivator, viscosity modifier, extreme pressure agent,demulsifier, seal swelling agent, or a mixture of two or more thereof.36. The lubricant or functional fluid composition of claim 33 whereinthe lubricant or functional fluid composition comprises a greasecomposition, the grease composition comprising lithium hydroxide,lithium hydroxide monohydrate, or a mixture thereof.
 37. A fuelcomposition comprising the composition of claim
 1. 38. The fuelcomposition of claim 37 wherein the fuel composition further comprises anormally liquid fuel.
 39. The fuel composition of claim 38 wherein thenormally liquid fuel is derived from petroleum, crude oil, aFischer-Tropsch process, coal, natural gas, oil shale, biomass, or amixture of two or more thereof.
 40. The fuel composition of claim 38wherein the normally liquid fuel comprises a synthetic fuel.
 41. Thefuel composition of claim 37 wherein the fuel composition comprisesgasoline or a middle distillate fuel.
 42. The fuel composition of claim37 wherein the fuel composition comprises kerosene, jet fuel, dieselfuel, fuel oil, heating oil, naphtha, or a mixture of two or morethereof.
 43. The fuel composition of claim 37 wherein the fuelcomposition further comprises: one or more functional additives, the oneor more functional additives, comprising a cold flow improver additivefor increasing horsepower; additive for improving fuel economy; additivefor lubricating and reducing wear of engine components; additive forcleaning and preventing deposit buildup; additive for reducing smoke andparticulate emissions; additive for removing water; additive forreducing rust and corrosion; additive for upgrading and stabilizing thefuel; additive for improving storage and combustion capabilities;antioxidant; antistatic agent; corrosion inhibitor; fuel system icinginhibitor; cold flow improver; biocide; metal deactivator; additive forreducing fuel line and filter clogging; additive for improving fuelatomization; additive for reducing deposits on burner nozzles; additivefor enhancing flame stabilization; additive for improving combustion;additive for reducing soot formation; additive for neutralizing vanadiumand sodium; additive for improving heat transfer; additive for reducingthe formation of sulfur trioxide; additive for reducing stacktemperatures; additive for reducing carbon monoxide, oxygen and/orunburnt hydrocarbon in stack gases; additive for reducing fuelconsumption; polar compound for dispersing paraffins; oil-solubleamphiphile; pour point depressant; dewaxing additive; sludge inhibitor;dehazer; additive for reducing cloud point; or a mixtures of two or morethereof.
 44. A composition comprising the composition of claim 1, andfurther comprising water, solvent, thixotropic additive, pseudoplasticadditive, rheology modifier, anti-settling agent, leveling agent,defoamer, pigment, dye, plasticizer, viscosity stabilizer, biocide,viricide, fungicide, crosslinker, humectant, surfactant, detergent,soap, fragrance, sweetener, alcohol, food product, food additive, or amixture of two or more thereof.
 45. The composition of claim 44 whereinthe composition is in the form of a liquid, a solid, or a mixturethereof.
 46. The composition of claim 1 wherein the functionalizedmonomer comprises a natural oil derived unsaturated fatty acid,unsaturated fatty ester, polyunsaturated fatty acid, polyunsaturatedfatty ester, or a mixture of two or more thereof.
 47. The composition ofclaim 1 wherein the functionalized monomer comprises a natural oilderived unsaturated monoglyceride, unsaturated diglyceride, unsaturatedtriglyceride, or a mixture of two or more thereof.
 48. The compositionof claim 1 wherein the functionalized monomer comprises an alkene chainwith a terminal functional group, the alkene chain being: an alkenechain of about 10 to about 30 carbon atoms and a carbon-carbon doublebond between the C₉ and C₁₀ carbon atoms in the alkene chain; or analkene chain of about 8 to about 30 carbon atoms and a carbon-carbondouble bond between the C₆ and C₇ carbon atoms in the alkene chain; oran alkene chain of about 12 to about 30 carbon atoms and a carbon-carbondouble bond between the C₁₁ and C₁₂ carbon atoms in the alkene chain; oran alkene chain of about 14 to about 30 carbon atoms and a carbon-carbondouble bond between the C₁₃ and C₁₄ carbon atoms in the alkene chain; oran alkene chain of about 14 to about 30 carbon atoms and carbon-carbondouble bonds between the C₉ and C₁₀ carbon atoms and between the C₁₂ andC₁₃ carbon atoms in the alkene chain; or an alkene chain of about 16 toabout 30 carbon atoms and carbon-carbon double bonds between the C₉ andC₁₀ carbon atoms, between the C₁₂ and C₁₃ carbon atoms, and between C₁₅and C₁₆ carbon atoms in the alkene chain; or an alkene chain of about 16to about 30 carbon atoms and carbon-carbon double bonds between the C₆and C₇ carbon atoms, between the C₉ and C₁₀ carbon atoms, between theC₁₂ and C₁₃ carbon atoms, and between the C₁₅ and C₁₆ carbon atoms inthe alkene chain.
 49. The composition of claim 1 wherein thefunctionalized monomer is derived from vegetable oil, algae oil, fungusoil, animal oil or fat, tall oil, sucrose, lactose, glucose, fructose,or a mixture of two or more thereof.
 50. The composition of claim 1wherein the functionalized monomer is derived from canola oil, rapeseedoil, coconut oil, corn oil, cottonseed oil, olive oil, palm oil, peanutoil, safflower oil, sesame oil, soybean oil, sunflower seed oil, linseedoil, palm kernel oil, tung oil, jatropha oil, mustard oil, camellinaoil, pennycress oil, castor oil, coriander oil, almond oil, wheat germoil, bone oil, lard, tallow, poultry fat, algae oil, yellow grease, fishoil, sugar cane, sugar beet, corn syrup, or a mixture of two or morethereof.
 51. The composition of claim 1 wherein the functionalizedmonomer is derived from a natural oil, the natural oil comprisingrefined, bleached and/or deodorized natural oil.
 52. The composition ofclaim 51 wherein the refined, bleached and/or deodorized natural oilcomprises refined, bleached and/or deodorized soybean oil.
 53. Thecomposition of claim 1 wherein the functionalized monomer comprises anestolide.
 54. The composition of claim 1 wherein the functionalizedmonomer is derived from an estolide.
 55. The composition of claim 1wherein the functionalized monomer is derived from a metathesizednatural oil or metathesized natural oil derived unsaturated carboxylicacid and/or ester.
 56. The composition of claim 55 wherein themetathesized natural oil or metathesized natural oil derived unsaturatedcarboxylic acid and/or ester is made by reacting one or more naturaloils and/or natural oil derived unsaturated carboxylic acids and/oresters in the presence of a metathesis catalyst.
 57. The composition ofclaim 56 wherein the metathesized natural oil or metathesized naturaloil derived unsaturated carboxylic acid and/or ester is made by reactingone or more natural oils and/or natural oil derived unsaturatedcarboxylic acids and/or esters with another olefinic compound in thepresence of a metathesis catalyst.
 58. The composition of claim 1wherein the functionalized monomer is derived from a metathesizednatural oil, the metathesized natural being made by reacting a naturaloil and/or natural oil derived unsaturated carboxylic acid and/or esterin the presence of a metathesis catalyst to form a first metathesizednatural oil; and then reacting the first metathesized natural oil in aself-metathesis reaction to form another metathesized natural oil, orreacting the first metathesized natural oil in a cross-metathesisreaction with a natural oil and/or natural oil derived unsaturatedcarboxylic acid and/or ester to form another metathesized natural oil.59. The composition of claim 55 wherein the metathesized natural oil isformed in the presence of a metathesis catalyst, the metathesis catalystcomprising a metal carbene catalyst based upon ruthenium, molybdenum,osmium, chromium, rhenium, and/or tungsten.
 60. The composition of claim55 wherein the metathesized natural oil is formed in the presence of ametathesis catalyst, the metathesis catalyst being represented by thefollowing formula (I)

wherein: M is ruthenium, molybdenum, osmium, chromium, rhenium, and/ortungsten; L¹, L² and L³ are neutral electron donor ligands; n is 0 or 1,such that L³ may or may not be present; m is 0, 1, or 2; X¹ and X² areanionic ligands; and R¹ and R² are independently selected from hydrogen,hydrocarbyl, substituted hydrocarbyl, heteroatom-containing hydrocarbyl,substituted heteroatom-containing hydrocarbyl, and functional groups,wherein any two or more of X¹, X², L¹, L², L³, R¹, and R² can be takentogether to form a cyclic group, and further wherein any one or more ofX¹, X², L¹, L², L³, R¹, and R² may be attached to a support.
 61. Thecomposition of claim 60 wherein M is Ru, W and/or Mo.
 62. Thecomposition of claim 55 wherein the metathesized natural oil is formedin the presence of a metathesis catalyst, the metathesis catalyst beingrepresented by the formula

wherein: M is a Group 8 transition metal; L¹, L² and L³ are neutralelectron donor ligands; n is 0 or 1, such that L³ may or may not bepresent; m is 0, 1, or 2; X¹ and X² are anionic ligands; and R¹ and R²are independently selected from hydrogen, hydrocarbyl, substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups, wherein anytwo or more of X¹, X², L¹, L², L³, R¹, and R² can be taken together toform a cyclic group, and further wherein any one or more of X¹, X², L¹,L², L³, R¹, and R² may be attached to a support; X and Y areindependently N, O, S, or P; p is zero when X is O or S; q is zero whenY is O or S; p is 1 when X is N or P; q is 1 when Y is N or P; and Q¹,Q², Q³ and Q⁴ are independently linkers, and w, x, y and z areindependently zero or
 1. 63. The composition of claim 55 wherein themetathesized natural oil is formed in the presence of a metathesiscatalyst, the metathesis catalyst being represented by one or more ofthe following formulae

wherein: L¹ is a neutral electron donor ligand; X¹ and X² areindependently anionic ligands; and M is a Group 8 transition metal. 64.The composition of claim 55 wherein the metathesized natural oil isformed in the presence of a metathesis catalyst, the metathesis catalystbeing represented by one or more of the following formulae (VII),(VIII), (IX) or (X):

wherein: M is a Group 8 transition metal; L¹, L² and L³ are neutralelectron donor ligands; r and s are independently zero or 1; t is aninteger in the range from zero to 5; X¹ and X² are anionic ligands; andR¹ and R² are independently selected from hydrogen, hydrocarbyl,substituted hydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups, wherein anytwo or more of X¹, X², L¹, L², L³, R¹, and R² can be taken together toform a cyclic group, and further wherein any one or more of X¹, X², L¹,L², L³, R¹, and R² may be attached to a support; Y is a non-coordinatinganion; Z¹ and Z² are independently selected from —O—, —S—, —NR²—, —PR²—,—P(═O)R²—, —P(OR²)—, —P(═O)(OR²)—, —C(═O)—, —C(═O)O—, —OC(═O)—,—OC(═O)O—, —S(═O)—, and —S(═O)₂—; and Z³ is a cationic moiety.
 65. Thecomposition of claim 55 wherein the metathesized natural oil is formedin the presence of a metathesis catalyst, the metathesis catalyst beingrepresented by the formula

wherein: X¹ and X² are anionic ligands; L¹ is a neutral electron donorligand; R¹ is selected from hydrogen, hydrocarbyl, substitutedhydrocarbyl, heteroatom-containing hydrocarbyl, substitutedheteroatom-containing hydrocarbyl, and functional groups; Y is apositively charged Group 15 or Group 16 element substituted withhydrogen, C₁-C₁₂ hydrocarbyl, substituted C₁-C₁₂ hydrocarbyl;heteroatom-containing C₁-C₁₂ hydrocarbyl, or substitutedheteroatom-containing hydrocarbyl; and Z⁻ is a negatively chargedcounterion.
 66. The composition of claim 55 wherein the metathesizednatural oil is formed in the presence of a metathesis catalyst, themetathesis catalyst being ruthenium (II)dichloro(3-methyl-1,2-butenylidene)bis(tricyclopentylphosphine);ruthenium (II)dichloro(3-methyl-1,2-butenylidene)bis(tricyclohexylphosphine);ruthenium (II) dichloro(phenylmethylene)bis(tricyclohexylphosphine);ruthenium (II)[1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(triphenylphosphine);ruthenium (II) dichloro(vinylphenylmethylene)bis(tricyclohexylphosphine); ruthenium (II)dichloro(tricyclohexylphosphine)(o-isopropoxyphenylmethylene); and/orruthenium (II)(1,3-bis-(2,4,6-trimethylphenyl)-2-imidazolidinylidene)dichloro(phenylmethylene)(bis3-bromopyridine).
 67. The composition of claim 55 wherein themetathesized natural oil is formed in the presence of a metathesiscatalyst, the metathesis catalyst being represented by structures 12, 14or 16, where Ph is phenyl, Mes is mesityl, and Cy is cyclohexyl:


68. The composition of claim 55 wherein the metathesized natural oil isformed in the presence of a metathesis catalyst, the metathesis catalystbeing represented by structures 18, 20, 22, 24, 26 or 28 where Ph isphenyl, Mes is mesityl, py is pyridyl, Cp is cyclopentyl and Cy iscyclohexyl:


69. The composition of claim 55 wherein the metathesized natural oil isformed in the presence of a metathesis catalyst, the metathesis catalystbeing represented by one or more of the following structures

wherein Ph represents phenyl, Cy represents cyclohexane, Me representsmethyl, nBu represents n-butyl, i-Pr represents isopropyl, py representspyridine (coordinated through the N atom), and Mes represents mesityl(i.e., 2,4,6-trimethylphenyl).
 70. The composition of claim 55 whereinthe natural oil or natural oil derived unsaturated carboxylic acidand/or ester is partially hydrogenated prior to the reaction in thepresence of the metathesis catalyst.
 71. The composition of claim 55wherein the metathesized natural oil comprises from 1 to about 100, orfrom 2 to about 50, or from 2 to about 30, or from 2 to about 10metathesis repeating groups.
 72. The composition of claim 55 wherein themetathesized natural oil comprises a metathesis dimer, metathesistrimer, metathesis tetramer, metathesis pentamer, metathesis hexamer,metathesis heptamer, metathesis octamer, metathesis nonamer, metathesisdecamer, or a mixture of two or more thereof.
 73. The composition ofclaim 1 wherein the maleic anhydride reacts with one or morecarbon-carbon double bonds in the hydrocarbyl group.
 74. The compositionof claim 1 wherein the maleic anhydride reacts in an ene reaction withone or more carbon-carbon double bonds in the hydrocarbyl group.
 75. Thecomposition of claim 1 wherein the maleic anhydride reacts with thecarbon atoms of one or more carbon-carbon double bonds in thehydrocarbyl group.
 76. A lubricant or functional fluid composition,comprising: an alcohol ester derived from the reaction of a malienatedmethyl 9-decenoate with iso-amyl alcohol; a polyalphaolefin; a hinderedaryl amine; and a polyisobutenyl succinic anhydride based dispersant.